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PROPYLENE POLYMERS
Introduction
The stereospecic polymerization of propylene by Giulio Natta in 1954 is one of
the most commercially signicant scientic breakthroughs in polymer chemistry.
Nattas discovery that a Ziegler catalyst could be used to produce highly isotactic polypropylene led to the rst commercial processes for the production of this
polymer by Montecatini in Italy and Hercules in the United States in 1957. The
attractive properties and relatively low cost of polypropylene produced using this
technology led to its rapid commercial acceptance. Consequently, Karl Ziegler and
Giulio Natta were awarded the Nobel Prize in Chemistry in 1963. The commercial
potential of olen polymerization was recognized by many of the leading companies, leading to a tremendous amount of activity and the invention of a number
of competing technologies in the early 1950s. These technologies were not economically competitive with those based on ZieglerNatta catalysts. However, the
competing claims of a number of companies led to a massive patent interference
in the United States that continued for almost 30 years, eventually resulting in
the award of a U.S. patent for the composition of matter of crystalline polypropylene to Hogan and Banks of Phillips Petroleum in 1983. Continued interest in
olen polymerization led to the invention of the supported high yield, high stereoregularity catalyst systems by Montedison and Mitsui Petrochemical. This led
to the development of a number of low cost polymerization processes, spurring a
dramatic increase in production capacity. Today, these catalyst systems are used
to produce polypropylene in every major region of the world. The use of homogeneous organometallic (metallocene) olen polymerization catalysts has led to
the development of a number of unique propylene polymers. Currently, these
polymers are produced in relatively limited amounts for a number of specialty
applications.
Polypropylene is one of the most widely used polymers in the world because
of the widespread availability and low cost of monomer, low manufacturing cost,
and attractive polymer properties. These properties can be modied to be suitable
for a wide variety of applications. Polypropylene can be processed by almost all
commercial fabrication techniques. Approximately 30,000,000 ton was consumed
worldwide in 2001.
Encyclopedia of Polymer Science and Technology. Copyright John Wiley & Sons, Inc. All rights reserved.

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Table 1. Physical Properties of Propylene

Property
Molecular weight
Boiling point at 101.3 kPaa , C
Melting point, C
Critical temperature, C
Critical pressure, MPab
Critical density, g/mL
Critical compressibility
Dipole moment, 10 30 Cmc
Refractive index, nD
Explosion limit, % by volume in air
Lower
Upper
Autoignition temperature, C
Solubility in water (at 20 C, 101.3 kPaa ), mL gas/100 mL

Value

Reference

42.078
47.7
185.3
92
4.65
0.233
0.275
1.3
1.3567

1
3
3
1
1
2
3
3
3

2.4
11.1
224
44.6

1
1
1
3

a To

convert kPa to mm Hg, multiply by 7.5.

convert MPa to atm, multiply by 9.87.
c To convert Cm to D, divide by 3.336 x 10 30 .
b To

Monomer
Properties. Propylene is an olen hydrocarbon that is a gas under ambient conditions but is normally stored as a liquid under pressure. The physical
properties of propylene are given in Table 1. Thermodynamic properties are widely
reported in the literature. Vaporliquid equilibria of mixtures of propylene with
other hydrocarbons and hydrogen are accurately represented by correlations for
hydrocarbon mixtures, such as the ChaoSeader correlation.
The reactivity of propylene is a result of the olenic double bond in
H2 C CHCH2 , which gives rise to addition reactions. Consequently, propylene
is used in the synthesis of many industrially important compounds, including
propylene oxide, acrylonitrile, cumene, and isopropyl alcohol. The consumption of
propylene in the production of polymers, however, is greater than the total for all
other chemicals. Propylene is also used in alkylating feedstocks for gasoline.
Manufacture. The major commercial sources of propylene are processes
for the cracking of hydrocarbons. Initially, these processes were designed for the
manufacture of other products, and propylene was considered an undesirable byproduct. Now, propylene is often an equally desirable co-product. Ethylene is produced by the steam cracking of hydrocarbons at high temperatures and very short
residence times. The two most common feedstocks are naphtha and ethane. This
process produces a variety of by-products; the ratio of ethylene to by-products is
dependent on the type hydrocarbon feedstock and the reaction conditions. Propylene production is higher when naphtha is used as a feedstock rather than ethane.
Catalytic cracking of hydrocarbons is often used to increase the production of gasoline in oil rening. Increasing consumption of gasoline in the United States has
led reners to increase the severity of the cracking process, resulting in an increase of the production of propylene as a by-product. Consequently, the ratio of

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Table 2. Recommended Maximum Limits of Impurities

in Propylene Used in Polymerizationa
Impurity
Acetylene, ppm vol
Methylacetylene, ppm vol
Propadiene, ppm vol
Butadiene, ppm vol
Green Oils (C6-C12), ppm vol
Oxygen, ppm vol
CO, ppm vol
CO2 , ppm vol
COS, ppm vol
Total sulphur, ppm wt
Methanol, ppm vol
Isopropanol, ppm vol
Water, ppm wt
Arsine, ppm vol
Phosphine, ppm vol
Ammonia, ppm wt
a Source:

Maximum limit
5
3
5
50
20
2
0.03
5
0.02
1
5
15
2
0.03
0.03
5

Basell.

propylene isolated from reneries to propylene from steam cracking is greater

in the United States than in Western Europe and other parts of the world. The
propylene isolated from the cracking processes is puried by distillation to remove
propane and other impurities. Propylene is commercially available as chemical
grade (approximately 95% propylene) and polymerization grade (>99.5% propylene) where propane is the major impurity. However, the suitability of propylene
as polymerization monomer is dependent on the levels of trace impurities rather
than on the propane content. Commonly occurring impurities are acetylenes, dienes, CO, COS, water, and alcohols. These impurities affect the activity and stereospecicity of propylene polymerization catalysts. Typical limits for the level of
impurities acceptable in polymerization grade propylene are given in Table 2.
Propylene is also produced by the metathesis of butene and ethylene. Usually,
this process is installed as an addition in a renery or steam cracking facility to
increase the production of propylene. The rst commercial metathesis process for
the production of propylene was developed by Phillips, and is now licensed by ABB
Lummus.
The relative abundance of propane and other light hydrocarbons in certain
locations has increased interest in the production of propylene by the catalytic
dehydrogenation of propane. Currently only a few propane dehydrogenation
plants are operating, producing a small fraction of the world supply of propylene; however, it is anticipated that propane dehydrogenation will be the major
source of propylene in the Middle East. The two major processes available are the
Caton process originally developed by Houdry and now licensed by ABB Lummus and the Oleex process licensed by UOP. Natural gas can be used as the
feedstock for the production of propylene by adding a Lurgi MTP process facility
to a conventional methanol plant.

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Transportation, Storage, and Handling. Propylene is stored and transported as a liquid under pressure The preferred method of transporting propylene is through pipelines. Commercial quantities of propylene are also shipped
by tanker and rail. The most extensive pipeline system for the transportation of
propylene is in the Gulf Coast region of the United States. This pipeline system is
also connected to a series of underground brine caverns used for propylene storage.
Pressure vessels are also used for the storage of propylene.
Propylene is a ammable gas under normal ambient conditions and is not
hazardous at low concentrations, but is an asphyxiant, which is a concern in closed
environments. Direct contact with liquid propylene can cause skin burns from
freezing. Fire or explosion is the greatest potential hazard associated with the
storage and handling of propylene. Care must be exercised to avoid creating an
explosive atmosphere when disconnecting lines and unloading vessels containing
propylene. Explosions of vapor clouds formed from large leaks of liquid or gaseous
propylene are the greatest potential hazard. The re and explosion hazards associated with propylene are similar to those of propane and liquied petroleum gas
(LPG).

Molecular Structure
The unique feature of propylene polymerization, versus ethylene polymerization,
is the symmetry of the monomer insertion into the growing polymer chain. It is
the presence of the methyl group in the propylene monomer that is responsible for
this difference. This gives the monomer insertion an orientation (the monomer has
a head and a tail) and a stereochemical conguration with respect to the other
units in the chain backbone. Regularity with respect to monomer orientation is
termed the regiospecicity of the polymerization. Regularity of the methyl group
placement relative to the other methyl groups along the chain backbone is termed
the stereospecicity of the polymerization. The three limiting classications of
stereospecicity in polypropylene (PP) are illustrated in Figure 1. In isotactic
polypropylene (iPP), all of the methyl groups have the same conguration with
respect to the polymer backbone. In syndiotactic polypropylene (sPP), the methyl
groups have an alternating conguration. Atactic polypropylene (aPP) has a random conguration. An additional conguration, hemi-isotactic polypropylene, is
discussed elsewhere (4). iPP is overwhelmingly the most commercially signicant
form of PP. In practice, the degree of stereoregularity (and tacticity microstructure) can vary considerably within these general classications. For the specic
case of isotactic polymerization, Figure 2 shows three idealized limiting sample
microstructures. Figure 2a shows a case where an isolated stereo error is immediately corrected along the growing chain. Figure 2b shows a case where a stereo
error is propagated along the growing chain, and Figure 2c shows an iPP/aPP
multiblock structure (57). Figure 2a is most common. Further discussions of
stereo defects are available in the literature (422). In general terms, stereoregularity (or stereospecicity) refers to the content of defects that disrupt the regular
placement of methyl groups. The intrachain defect content can also vary widely
between chains (interchain distribution) (23) for different catalyst systems. The

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Fig. 1. Polypropylene stereochemical congurations: (a) isotactic; (b) syndiotactic;

(c) atactic.

control of stereoregularity by catalyst and polymerization process is a critical determinant of PP properties.

Kinetic arguments suggest that iPP polymerization shows a strong preference for primary head-to-tail insertion of monomer into the growing chain
(2426). Regioirregular insertion of monomer renders the active site kinetically
dormant (2430), and its incorporation in the growing polymer chain occurs infrequently. With ZieglerNatta polymerization catalysts, regio misinsertion errors
are generally not present in the isotactic fraction (30). Metallocene polymerization catalysts can show appreciable levels of regio misinsertion errors in chains of
high stereospecicity (4,27,3141) (see METALLOCENES; SINGLE-SITE CATALYSTS).

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Fig. 2. Sample tacticity microstructures in isotactic polymerization: (a) isolated stereo

error is corrected in growing chain; (b) stereo error is propagated in growing chain; (c) an
iPP/aPP multi-block structure.

The stereo- and regioregularity of PP is best characterized by solution

C NMR spectra (42). These spectra can also provide information on the polymerization mechanism (4,7,9,11,12,1422,30), and have been modeled in terms
of the interchain tacticity distribution (14,4345). Infrared spectroscopy (IR) has
also been used to characterize the stereospecicity of iPP. Commonly the ratio of
the 998 and 973 cm 1 band absorbance is used (46,47). The result is sensitive
to thermal history (46). Solvent fractionation techniques are commonly used in
industrial practice. These methods are based on the fact that chains with varying stereospecicity have different crystallinity and solubility in hydrocarbon solvents. In nominally isotactic PP, the atactic fractions of the interchain tacticity distribution are soluble, whereas the isotactic fractions are not. The isotactic
index suggested by Natta represents the percentage of polymer insoluble in boiling
n-heptane (48). Other procedures require preliminary total dissolution of the polymer in high boiling hydrocarbons such as xylene, and subsequent cooling in order
to separate the precipitated crystalline portion (an example is ASTM D5492-94).
The insoluble fraction is a measure of the stereospecicity. Often the term stereoblock is used to refer to fractions of the interchain distribution of intermediate
solubility. Related solvent fractionation techniques include preparative and analytical temperature rising elution fractionation (TREF) (49). The use of pulsed
proton solid-state NMR has been demonstrated as an alternative to solubility measurements of stereoregularity (50). Other secondary measurements which probe
melting and/or crystallinity behavior can also be applied.
In addition to tacticity, important additional parameters of the PP chain
which inuence properties include the molecular weight, polydispersity, and
composition and comonomer distribution in blends and copolymers. PP, like
all synthetic and most natural polymers, consists of a distribution of macromolecules of different lengths. Therefore, the polymers exhibit a molecular weight
13

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distribution. The number-average molecular weight (M n ) is determined by gelpermeation chromatography (GPC), more generally referred to as size-exclusion
chromatography (51). Because of the strength of the GPC technique, the older
techniques of osmometry (52,53), cryoscopy (54), and ebulliometry (54) are less
commonly used today. For PP, the GPC method typically utilizes high temperatures (135145 C) in solvents such as o-dichlorobenzene and trichlorobenzene.
The weight-average molecular weight (M w ) can be obtained by light scattering
(55) and GPC. Higher moments of the molecular weight distribution can also be
obtained by GPC. The viscosity-average molecular weight M can be obtained by
measurement of the solution intrinsic viscosity []0 (52). M and []0 are related
by the MarkHouwink equation:
[]0 = K(M )a
Generally, values of M lie between M n and M w values. Values of the constant
K and exponent a are determined by calibration with homogeneous fractions of
known molecular weight for specic solvent/temperature conditions. In practice,
for polypropylene, homogeneous fractions are not available and values for some
moment of the molecular weight distribution (M n or M w ) are used in equation 1
on an empirical basis to determine K and a. This allows for the correlation of
viscosity to molecular weight, though corrections need to be applied for samples
with polydispersity much different from the correlation standards (56). Representative values using M w from relatively narrow polydispersity fractions in decalin
at 135 C are K = 2.38 10 4 , a = 0.725 (57) and K = 1.01.10 10 4 , a = 0.80
(58,59), and in tetralin at 135 C are K = 9.42 10 5 , a = 0.784 (60). A common industrial measure of molecular weight is the melt-ow rate (MFR) (ASTM D1238),
which is related to the melt viscosity. The MFR technique measures the amount
of molten polymer extruded by a standardized apparatus in 10 min. Higher MFR
values are obtained for lower molecular weight polymer. The breadth of the molecular weight distribution (polydispersity) has a large effect on polymer properties.
The polydispersity is commonly characterized by the ratio M w /M n as measured
by GPC or by semiempirical correlation of the dynamic melt oscillitory shear behavior of the polymer (61). This ratio has a value of 1 for macromolecules of equal
molecular weight (monodisperse) and increases with increasing polydispersity.
Rheological measurements, including the steady-state compliance, can be very
sensitive to higher moment components (62) important in ow processes.
The molecular structure of PP can be further modied by the introduction
of comonomers during the polymerization process, most commonly ethylene or
butene. This comonomer incorporation greatly expands the property range of PP.
Table 3 illustrates the broad range of copolymer microstructures possible for the
specic case of propyleneethylene copolymerization. Similar to the case of stereoregular defects in PP homopolymer, comonomer defects introduced into random PP copolymers (PP-RACO) can show an interchain composition distribution
depending on the catalyst and process. In some cases it can be advantageous,
in terms of quality and the process conditions, to achieve a homogeneous distribution of the comonomer molecules. Metallocene catalysts show a greater tendency for homogeneous comonomer incorporation (4). In this case, each chain, regardless of length, contains the same percentage of comonomer. Impact-modied

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Table 3. PropyleneEthylene Copolymerization Microstructure

Microstructurea
PPPPPPPPPPPPPPPP (PP)
PPPEPPPPPPPPEPPP (PP-RACO)
PPPPPPPP + EPEPEP (PP-EPR)
PPPPP + EPEP + EEEE (PP-EPR + PE)
EPEPPEEPEPEPEPE (EPR)
EEEPEEEEEEEPEEE (PE-RACO)
EEEEEEEEEEEEEEE (PE)
a P=

Products
Homopolymer polypropylene
Polypropylene randomly modied with
ethylene
Impact-resistant polypropylene
Impact-resistant polypropylene (with
polyethylene
Ethylenepropylene rubber (elastomer)
Polyethylene randomly modied with
propylene
Homopolymer polyethyle

propylene, E= ethylene.

copolymers (PP-EPR) are better described as polymer blends or alloys. The

composition of the PP-EPR formulations varies over a wide range in industrial
practice. However, a typical formulation would contain 6090% homopolymer (or
PP-RACO) and 1040% ethylenepropylene copolymer rubber (EPR) with ethylene concentration of 3060%. The EPR component has a lower glass-transition
temperature (T g ), lower crystallinity, and typically exists as a separate phase.
PP-EPR formulations were rst produced by mechanical blending of two components. Today they are commonly synthesized directly in a multistage process to
obtain better economics, and often better distribution of the elastomeric phase in
the polypropylene matrix and thus better quality. In some cases polyethylene is
present as a third phase. The characterization of PP copolymers is often complicated by the multiplicity of structural species present. An in-depth characterization requires knowledge of the distributions of molecular weight and composition.
Different solvent fractionation techniques are combined, and each fraction is analyzed. Composition is most frequently determined by solution 13 C NMR, by IR,
or inferred from secondary measurements which probe melting behavior, crystallinity, or glass-transition temperature.

Morphology
Crystallography and Polymorphism. The stereochemistry of PP plays
a critical role governing the packing of chains in the crystalline regions of the
morphology (qv). Figure 3 shows the wide-angle X-ray scattering (WAXS) patterns of iPP, sPP, and aPP (23). The regular molecular structure of iPP and sPP
readily enables crystallization of the chains, leading to well-dened crystalline reections differing in unit cell symmetry. aPP lacks a regular molecular structure,
and does not crystallize. This leads to a very broad and diffuse scattering from
X-rays. The iPP chain adopts a helical conformation in the crystalline unit cell, as
shown in Figure 4 (63). The helix repeats itself after three monomeric units, with
an identity period of 0.65 nm. Four helical arrangements are possible by rightor left-handed rotation about the central axis with unique (non-identical) up
and down inclinations independent of the handedness (23,64,65). The dominant

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Fig. 3. Wide-angle X-ray scattering (WAXS) patterns of iPP, sPP, and aPP. The shaded
region illustrates the separation of crystalline and amorphous scattering contributions.
Adapted from Ref. 23.

crystallographic form for iPP is the -form. The elementary unit cell of -form iPP
is monoclinic, containing 4 chains and 12 monomeric units with specic packing
of helical arrangements. Crystallographic densities are generally in the range of
0.9360.946 gm/cm3 . Representative cell constants are given in Table 4, and have
been reviewed elsewhere (23). The helical conformation of sPP differs from that
of iPP, and has an identity period of 0.74 nm. The elementary unit cell of the most
stable crystallographic form of sPP is orthorhombic, containing 4 chains and 16
monomeric units with specic packing of helical arrangements (23,64,6669). The
crystallographic density is 0.930 gm/cm3 . Representative cell constants are given
in Table 4 (69).

Table 4. Unit Cell Constants of Polypropylene

Cell constants

Isotactica

Syndiotacticb

Unit cell
a, nm
b, nm
c, nm

monoclinic
0.664
2.084
0.651
99.0

orthorhombic
1.45
1.12
0.74
90

a Averages from literature compilation of P2 /c space

1
group symmetry renements (23).
b From Ref. 69.

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Both iPP and sPP exhibit polymorphism, which is the tendency to crystallize
into different crystallographic forms depending on crystallization conditions.
In iPP, the dominant form is the -form. Other forms include the -, -, and
mesomorphic (smectic) forms. All of these crystalline forms maintain the
same helical conformation with 0.65 nm repeat distance, but differ in unit
cell symmetry, interchain packing, and structural disorder. The mesomorphic
form is formed by rapid quenching conditions, and has important property
implications, particularly in lm and ber applications. Crystallographically,
the mesomorphic form has disordered interchain packing relative to the other
polymorphic unit cell symmetries (65,70,71). The mesomorphic form converts
rapidly to the -form on heating (23). Formation of the -form results from the
addition of specic nucleators and additives, specic crystallization conditions,
crystallization under controlled temperature gradients, and in some cases crystallization under shear (20). The -form has lower unit cell density, higher rate
of crystallization, and lower apparent melting point relative to the -form which

Fig. 4. Chain conformation of isotactic polypropylene (iPP).

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is due, in-part, to its unique crystallography (64,72,73). The -form is rarely

observed in pure form in commercially signicant homopolymer from Ziegler
Natta catalysts under typical processing conditions. A variety of conditions for
-form formation are outlined below (23). The -form occurs in low molecular
weight fractions, homopolymer from some homogeneous (metallocene) catalysts
(7476), random copolymers, random copolymer and metallocene homopolymer
at high crystallization temperature (76), samples with high stereoblock content, and homopolymer crystallized at high pressure (77). Crystal structure
renements suggest that -form iPP has nonparallel chains (64,65,7881),
a conclusion not previously cited in polymeric crystal structure. Because of its
importance, further discussion of iPP morphology is restricted to the -form of
iPP.
sPP also exhibits polymorphism (23,64,6669,82,83). Polymorphism is related to both the intrachain conformation and interchain packing. Crystallization
at lower temperature can lead to defect structures relative to the unit cell symmetry of the dominant form (6668,8486). Other unit cell variations are formed from
sPP with low syndiospecicity (87,88), as-polymerized sPP (8992), sPP copolymers (92), oriented sPP (23,87,93), sPP crystallized at low temperature (94,95),
and nonhelical structures associated with cold drawing (87,96) and exposure of
cold drawn samples to solvent vapor (97).
Crystallinity. The degree of crystallininity varies between 0 for a completely amorphous material (such as aPP) and 1 for a completely crystalline material. As with most semicrystalline polymers (qv), the degree of crystallinity plays
a critical role in determining properties of PP. Commonly measured properties
such as modulus, yield stress, oxygen and moisture barrier resistance, and hardness, to name a few, all increase with increasing crystallinity. In iPP (and sPP)
tacticity is a critical factor inuencing the crystallinity (23,47,98). This is due to
the role of stereo defects in disrupting the length of the crystallizable isotactic
sequences. Details of the interchain tacticity distribution affect not only the crystallinity at room temperature, but also the partial melting behavior (and hence
crystallinity) at elevated temperature, inuencing hot drawing characteristics.
Solvent fractionation techniques, which separate the interchain tacticity distribution of the whole iPP homopolymer into fractions of varying tacticity, show that
the lower tacticity fractions have lower crystallinity (47). With metallocene catalysts (4,18,30), PP chain microstructure can now be varied continuously with
decreasing isospecic sequencing from iPP (stiff thermoplastic) to aPP (very low
modulus lacking dimensional integrity) to sPP (stiff thermoplastic) correlating
to changes of either isotactic or syndiotactic crystallinity. The crystallinity of
sPP is less than that of iPP with currently available catalysts. In addition to
tacticity, crystallinity generally increases with decreasing molecular weight (increased chain mobility), and is promoted by slower cooling rates from the melt.
It should be emphasized that the crystalline fraction of perfectly isotactic PP
is still much less than unity because of the long-chain nature. Copolymerization (PP-RACO in Table 3) is also used to modify the polymer crystallinity in a
controlled manner. In this case, the comonomer is the source of irregularity in
the polypropylene chain. The introduction of comonomer decreases crystallinity,
reduces stiffness and melting temperature, and increases impact resistance
(99).

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The degree of crystallinity is determined by a number of analytical techniques based on different criteria (see CRYSTALLINITY DETERMINATION). The most
widely used are fractional solubilization (previously discussed), density determination, X-ray diffraction, and thermal analysis. The density of iPP in the form varies between the limit of 100% amorphous ( a =0.850 to 0.855 g/cm3 ) and
100% crystalline ( c =0.936 to 0.946 g/cm3 ) (20). In this way, the measured mass
density gives a measure of the crystallinity. Values of are most often measured
by the density gradient technique (ASTM D1505-85). Similarly, dilatometric methods are used to measure variations of density as a function of temperature (100).
X-ray diffraction (101) is also widely used to determine PP crystallinity. Figure 3
shows the contributions of the crystalline scattering and amorphous scattering in
the unoriented pattern of the -form of iPP. The shaded region represents the area
attributable to the noncrystalline fraction. From the relationship of the peak area
to the total area, crystallinity can be evaluated by a number of numerical means
(101). Orientation complicates the analysis (101). Differential scanning calorimetry (DSC) provides useful information on PP structure by the determination of
related parameters, such as transition temperature, heat of fusion, crystallization temperature, and others. The crystalline fraction is given by the ratio of the
measured heat of fusion to the value for 100% crystalline material (see THERMODYNAMIC PROPERTIES OF POLYMERS). The shape of the melting curve gives information
on the melting distribution.
Lamellar and Spherulitic Morphology. The crystal habit of iPP quiescently crystallized from the melt, like other semicrystalline homopolymers, is that
of folded chain lamellae (Fig. 5). The lamellar thickness (lc ) increases with increasing crystallization temperature, and is generally in the range of 520 nm for
iPP. iPP in the -form exhibits a tendency, unique among semicrystalline polymers, to form a cross-hatched pattern (23,64). Radial lathlike lamellae coexist
with cross-hatched tangential lamellae oriented nearly orthogonal to the radial
direction. This homoepitaxy (102107) is related to the relatively modest mismatch between the c- and a-axis unit cell parameters (Table 4), and the detailed
molecular aspects have been reviewed (64). Spherulites are larger scale aggregates made up of the smaller scale lamellar building blocks. Depending on the

Fig. 5. Schematic of chain-folded lamellar structure in semicrystalline polymers.

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crystallization conditions, the dimensions of spherulites can vary from a few micrometers to 100 m, or larger. In the -form of iPP, there is a strong link between lamellar and spherulitic morphologies. The -form iPP spherulites have
been classied according to different optical characteristics in cross-polarized
light (106,108,109). The optical characteristic is highly sensitive to crystallization temperature and resin type, and has been linked to the lamellar morphology through the balance of cross-hatched radial and tangential lamellae
(23,103,104,106,109,110). Optical and mechanical properties depend on the dimension and number of spherulites, which can be modied with nucleating agents
that act as crystallization centers. Optical properties (such as clarity) improve
with decreasing spherulite size. The borders among spherulites can represent
weak zones (111), with large spherulites adversely affecting properties such as
impact. Unlike iPP, pronounced cross-hatched lamellar morphologies in bulk crystallized material appears limited in sPP (112,113). As with iPP, well-developed
small-angle X-ray (SAXS) long spacings, characteristic of well-developed lamellar
morphologies, are observed for sPP of high syndiospecicity (113116). In general terms, spherulite formation in as-polymerized metallocene based sPP tends
to be more restricted than in iPP (117119), and the spherulite-scale morphologies are generally smaller than in iPP in bulk-crystallized specimens. Spherulitic
growth rate measurements have been summarized (120), with rates lower than
those of ZieglerNatta iPP (113). Unique morphologies (relative to iPP) are observed in sPP with special preparation procedures, including a transition from
single-crystal like entities to spherulitic structures on cooling (68,117119).
Macromorphology and Processing Relationships. Other morphologies in iPP include the macroscopic phase morphologies in multiphase structures
such as rubber-modied iPP (an example being PP-EPR in Table 3), and additional morphologies associated with the specic method of polymer processing.
Unique morphologies and structure/processing relationships are associated with
ber, lm, and injection molding processes to name a few. In parts formed by the injection molding process, pronounced morphological gradients exist in a processed
part which can be crudely partitioned into highly oriented skin layers (near the
mold surface) and less oriented core layers (near the part center). These layers
can approach macroscopic dimensions (mm) depending on the part geometry,
resin, and molding conditions. The properties of moldings can often be correlated
to the orientation and crystallinity of the part (23,121). A literature review of
more detailed aspects of the morphology of iPP injection moldings is available
(23). In mixtures of iPP homopolymer and EPR (PP-EPR in Table 3), the two
components are generally immiscible in the melt. In the solid state, the rubber
has low glass-transition temperature (T g ) and imparts impact resistance to the
blend. The effectiveness of the rubber phase as an impact modier depends critically on the dispersion (particle size). The dispersion is a complex function of
(1) matrix and rubber phase composition, (2) viscosity ratio of matrix and dispersed phases, (3) compounding history, and (4) melt deformation history during
fabrication of the nal processed part (23). In impact-modied copolymers for injection molding applications, the dimension of the dispersed rubber phase in the
core (reduced melt deformation) is typically on the order of 0.52 m in formulations with optimal impact performance. Near the surface of moldings (high melt
deformation), highly anisotropic dispersed phase morphologies can be observed

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depending on blend composition. Generally rubber phase dispersion worsens (increased phase size) with increasing melt temperature and melt time prior to molding due to coalescence.
High speed melt spinning of bers represents another of the most common processing methods for iPP. The nal morphology results from the complex interrelationships of polymer structure (polydispersity, molecular weight,
tacticity) and processing conditions (melt temperature, melt throughput, spinnerette design, spin speed, cooling rate). For high spinning speeds, the orientation of melt-spun bers greatly exceeds that of injection-molded parts. The orientation of crystalline regions is greater than the non crystalline regions (122). As
the spinning speed increases, orientation increases. The orientation can be further increased with post-spinning drawing operations (122). As with unoriented
material, the as-spun ber shows alternating crystalline and amorphous regions
on lamellar size scales (1030 nm), but generally smaller than hot-drawn articles.
This periodicity is highly oriented along the ber axis, and characterized by a
high fraction of tie molecules (the same chain passing through several crystalline
regions).
Drawn lm, and more specically biaxially oriented polypropylene (BOPP)
lm, is another of the most common fabrication methods (see FILMS, MANUFACTURE; FILMS, ORIENTATION). During BOPP lm formation, a cast sheet of iPP is
drawn below the melting point in two directions. This drawing process creates a
lm of useful dimension while imparting desired properties such as barrier and
stiffness. These properties are related to the imposed orientation during drawing.
During unidirectional drawing of semicrystalline polymers at elevated temperature, the initial spherulitic morphology of the cast sheet is transformed to an
oriented brillar morphology (122125). The yielding process, during which the
lamellar crystallites are disrupted, is strongly correlated to the crystallinity at
the draw temperature. As with melt-spun bers, the orientation of the crystalline
regions is greater than that of the noncrystalline regions (122). Orientation is
generally much higher than in injection moldings. For BOPP, the molecular orientation is dominated by the transverse orientation stage for sequentially oriented
lm (126), and tends to be planar (126,127) for both sequential and simultaneous oriented lm. Generally, the lamellar crystals in the initial as-cast sheet are
highly disrupted in the nal BOPP lm.
Polymerization Particle Morphology. Morphological control of aspolymerized polymer particles inuences the polymerization process. Aspects of
the particle morphology include the shape, size, size distribution, and porosity.
Control of particle morphology is also a critical concern to technologies which
utilize the as-polymerized particle in subsequent polymerization processes (128).
Because of the replication phenomenon (129137), the morphological characteristics are strictly dependent on the catalyst. The catalyst reproduces its shape in
the polymer on an obviously greater scale according to its activity. The activity is
the quantity of polymer produced by a unit of catalyst.
The replication phenomenon of iPP polymerization from magnesium chloride
supported ZieglerNatta catalysts is illustrated in Figure 6. The polymer particle
has the same shape as the catalyst particle, although its diameter is approximately
20100 times larger. The growth of the polymer particle during polymerization has
been extensively modeled (129137). In the multigrain model (131135,137), the

Vol. 11

PROPYLENE POLYMERS

301

Fig. 6. ZieglerNatta catalyst particle (a) and corresponding polymer particle (b).

catalyst undergoes fragmentation into microparticles evenly distributed within

the macroscopic particle due to forces exerted by the growing polymer layers.
In ZieglerNatta catalysts, fragmentation occurs at very low polymer yields
(137139), which provides a large active surface from the beginning of polymerization. The growth of the macroparticle results from the cumulative uniform expansion of microparticle layers. Although the actual morphology of ZieglerNatta
polymerized particles shows a more complicated hierarchy than the two-level
approach of the multigrain model, a key feature is the replication of the porous
spherical catalyst morphology into a porous spherical polymer particle during
polymerization. In practice, a careful morphological analysis of the polymerization particle requires, beyond microscopic investigations, analyses of particle size
distribution (ASTM D1921-96), poured bulk density (ASTM D1895-96, Method A),
and pourability (ASTM D1895-96, Method A).

Thermodynamic Properties
Melting. The melting point of -form iPP is strongly inuenced by
the stereoregularity (19,23,47,99,140144) and regioregularity (4,33,34,145,146).
Melting point increases with improved regularity. T m0 is the theoretical equilibrium melting point of a perfect and innitely large crystal. This value exceeds
experimentally observed melting points because of kinetic effects leading to small
crystal size (23) (Fig. 5). The value of T m0 is sensitive to stereoregularity. However,
the value for 100% isotactic material is not expected to differ signicantly from
that of highly isotactic commercial materials (23). For highly regular materials,
literature summaries of T m0 suggest that values of 185188 C seem reasonable
(23), though there remains disagreement in the literature (147). Melting points in
the 160168 C range are typical for commercial homopolymer samples under normal analysis conditions. Introduction of comonomer (ethylene, butene, and higher
-olens) reduces the melting point, and can vanish at intermediate compositions

302

PROPYLENE POLYMERS

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as the material approaches an amorphous rubber (Table 3). Literature summaries

of the heat of fusion of 100% crystalline material,
H0 , generally lie in the range
of 148209 J/g (23). The most often applied values are clustered around 165 J/g
(77,140,148,149) and 209 J/g (150,151).
As with iPP, the melting point of sPP is highly sensitive to stereoregularity.
While comparison of T m0 for 100% syndiotactic sPP is ambigous, with current
catalysts and in current commercial sPP materials, the observed melting point
is generally less than that of ZieglerNatta iPP under practical crystallization
conditions when compared at comparable stereospecicity (23). This difference is
often of the order of 1015 C. Introduction of comonomer also reduces the melting
point of sPP. Syndiospecic copolymerization with butene has the unique feature of
being crystalline at all compositions because of the similarity of crystal structures
of sPP and syndiotactic polybutene (152). Literature summaries of
H0 lie in the
range of 105190 J/gm (23). Values in the lower end of this range agree with
extrapolated heats of fusion versus density (23) and X-ray crystallinity (116).
Glass-Transition Temperature. The value of the glass transition (qv)
temperature (T g ) is dependent on the crystallinity of the polymer, the molecular
weight, and the measurement techniques used. DSC measurements of T g for high
molecular weight aPP and sPP are generally similar and usually close to 0 C. The
DSC glass-transition temperature in highly stereospecic iPP is often difcult to
distinguish because of the high crystallinity. Transition temperatures are generally in the range of 13 to 0 C. Other techniques, such as dynamic mechanical
analysis, are often more sensitive to the T g of iPP. Copolymerization with ethylene reduces the glass-transition temperature. Figure 7 shows DSC measured T g
values of propylene/ethylene copolymers prepared with an aspecic catalyst. In
this case, all samples are noncrystalline and not affected by crystallinity. A similar trend is generally observed for isospecic and syndiospecic catalysts as well.
Copolymerization with butene is less effective at lowering the T g .
Heat Capacity and Thermal Expansion. Extensive tabulations of the
extrapolated heat capacities of crystalline and amorphous iPP as a function of
temperature are available (147). The specic volume (153) and heat capacity (154)
of iPP in the melt as a function of temperature and pressure, and typical thermal
expansion coefcients in the solid state as a function of temperature (151) are also
reported.

Chemical Properties
iPP is soluble in high boiling aliphatic and aromatic hydrocarbons at high temperature. sPP shows solubility at lower temperature and in lower boiling hydrocarbons. aPP shows the highest solubility of the three forms. Extensive chemical
resistance data is available for iPP (155). The high chemical resistance of iPP results in exceptional stain resistance, and has led to the use of iPP in automobile
batteries (156). iPP has outstanding resistance to water and other inorganic environments (155). iPP resists most strong mineral acids and bases, but like other
polyolens is subject to attack by oxidizing agents including 98% sulfuric acid
and 30% hydrochloric acid at high temperature (100 C), and fuming nitric acid
(ambient temperature) (155). Inorganic chemicals produce little or no effect over

Vol. 11

PROPYLENE POLYMERS

303

Fig. 7. Glass-transition temperature (T g ) versus ethylene concentration in propylene

ethylene random copolymer using aspecic catalyst (no crystallinity). Values were determined by differential scanning calorimetry (DSC).

a period of 6 months at temperatures up to 120 C (155). For organic media, absorption is greater for higher temperatures and decreased polarity, and is higher
in copolymers than in homopolymer.
PP reacts with oxygen in several ways, causing chain scission and brittleness
that is associated with the loss in molecular weight. This action is promoted by
high temperatures, light, or mechanical stress. A wide variety of stabilization
packages are added for protection, depending on the application (157).
The reactivity of iPP can also be usefully exploited. For example, treatment
with peroxides has led to controlled rheology resins (61,158,159) with reduced
molecular weight and narrow polydispersity relative to as-polymerized product
from ZieglerNatta catalysts. For a xed nal melt-ow rate (MFR), lower precursor MFR gives narrower polydispersity. These resins are used in some berspinning and injection-molding applications. The creation of radical sites along
the polymer backbone, most often through peroxide-based initiation, is also an
essential condition for many functionalization/grafting chemistries. The functionalization chemistry of post-polymerized iPP has been extensively reviewed
(160). The focus has been on the incorporation of polar functional groups into the
polymer chain and/or the graft polymerization of monomers which are generally
incompatible with ZieglerNatta catalysts. The incorporation of polar functionality has been sought to improve paintability, printability, and metal adhesion
characteristics (important to coatings); to act as coupling agents in composites
such as glass-reinforced iPP; to improve oxygen barrier resistance; and to act
as compatibilizers in polymer alloys. Recent advancements in metallocene and

304

PROPYLENE POLYMERS

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related transition metal catalysts are showing promise for the direct copolymerization of polar monomers with ethylene and propylene (161). Other chemical
modications include plasma and acid treatment technologies.
Radiation chemistry of PP has been extensively reviewed (162). Under suitable conditions, radiation treatment can lead to desirable branching reactions
(163) with rheological characteristics favorable for thermoforming, foaming, blow
molding, and extrusion coating. Resistance to radiation sterilization is an important requirement in some medical applications, and requires specialized formulation and stabilization packages.

Physical Properties
A vast number of PP grades are sold in the United States, including homopolymers
with varying molecular weight (melt-ow rate) and tacticity, lled grades, grades
with varying stabilization packages, and grades which incorporate comonomers
with varying architecture (Table 3). The basic categories of iPP polymers are homopolymers, random copolymers, impact or heterophasic copolymers, and lled
polymers. A number of grades are approved for food contact (164). Many polymers carry a UL94 ammability class HB rating (164), and some specialized formulations have improved ratings. Additional specialty grades include nucleated
polymers for improved clarity and mechanical properties, radiation-resistant formulations, chemically visbroken controlled rheology grades (61,158,159), high
melt strength grades, and a large number of formulations with specialized additive functions including slip agents, antiblocking agents, antistats, and pigments
to name a few (157). Standardized test methods such as ASTM or ISO are used in
commercial specications. The properties that distinguish iPP from high density
polyethylene are high heat distortion temperature, stiffness, hardness, and lower
density.
Properties of various homopolymer grades are given in Table 5. In this
table, polymer molecular weight and polydispersity is tailored to give the best
processing characteristics for each fabrication process. The polymers shown in
Table 5 are produced by direct polymerization. Higher melt ow grades, and
controlled rheology grades with narrow polydispersity, can be important in
other applications, including bers. Narrow polydispersity resins can also be
produced by metallocene catalysts (4). These catalysts can also produce iPP
with a narrow interchain tacticity distribution and low levels of extractables.
High crystallinity (tacticity) grades, and high polydispersity grades, provide
additional stiffness and higher heat distortion temperature in injection molding
applications (23,120,166,167). Properties of selected random copolymer grades
are given in Table 6. These copolymers have ethylene as the comonomer,
although butene copolymerization is also possible. The stiffness of these polymers is lower than that of homopolymers. The impact resistance is improved,
particularly at refrigeration temperatures. Clarity is also enhanced. The low
melting point allows the use of some copolymer grades as sealant layers in
PP lms. Properties of impact-resistant, or heterophasic, copolymers are given
in Table 7. Much of this class of material is used in injection-molding applications,

Table 5. Properties of Polypropylene Homopolymersa

Melt
ow,
(g/10
min)
(ASTM
D1238)
305

0.5
4
12
22
35
a Ref.

Tensile
strength,b
Mpac
(ASTM
D638)

Elongation,b
% (ASTM
D638)

Flexural
modulus
1%
secant,
Mpac
(ASTM
D790A)

33
34
34
36
32

13
12
10
10
12

1200
1400
1400
1500
1200

165.
yield.
c To convert Mpa to psi, multiply by 145.
d To convert kPa to psi, multiply by 0.145.
e To convert J/m to ftlbf/in., divide by 53.38.
b At

Deection
tempeature
at 455
kPa,d C
(ASTM
D648)

Notched
Izod
Impact
at 23 C,
J/me
(ASTM
D256A)

Rockwell
hardness,
R
(ASTM
D785A)

Products/Applications

96
93
92
93
95

81
39
35
34
32

86
86
88
93
89

Extrusion, sheet, proles

Injection molding, general-purpose
Injection molding, general-purpose
Injection molding, general-purpose, thin wall
Controlled rheology injection molding, thin-wall

Table 6. Properties of Polypropylene Random Copolymersa,b

Tensile
strength,c
Mpad
(ASTM
D638)

Elongation,c
% (ASTM
D638)

Flexural
modulus
1%
secant,
Mpad
(ASTM
D790A)

28

13

940

79

330

6.5
11

28
30

13
13

920
1000

76
84

56
66

35

28

13

940

83

140

Melt
ow,
(g/10
min)
(ASTM
D1238)
306

a Ref.

165
on ethylene comonomer.
c At yield.
d To convert Mpa to psi, multiply by 145.
e To convert kPa to psi, multiply by 0.145.
f To convert J/m to ftlbf/in, divide by 53.38.
b Based

Deection
tempeature
at 455
kPa,e C
(ASTM
D648)

Notched
Izod
Impact
at 23 C,
J/mf
(ASTM
D256A)

Products/Applications
High clarity blow molding, extrusion,
thermoforming
High clarity cast lm
High clarity injection molding and
injection-stretch blow molding
Controlled rheology high clarity injection molding

Table 7. Properties of Polypropylene Impact Copolymersa,b

Tensile
strength,c
Mpad
(ASTM
D638)

Elongation,c
% (ASTM
D638)

Flexural
modulus
1%
secant,
Mpad
(ASTM
D790A)

0.45
2
4
35

27
27
27
27

11
9
8
6

1100
1200
1200
1400

88
90
90
100

No break
270
110
70

50

26

1200

107

42

4
8
22

21
26
24

8
8
7

1000
1200
1000

81
87
83

No break
100
100

12

22

900

82

340

Melt
ow,
(g/10
min)
(ASTM
D1238)

307

a Ref.

165
on ethylene comonomer.
c At yield.
d To convert Mpa to psi, multiply by 145.
e To convert kPa to psi, multiply by 0.145.
f To convert J/m to ftlbf/in, divide by 53.38.
b Based

Deection
tempeature
at 455
kPa,e C
(ASTM
D648)

Notched
Izod
Impact
at 23 C,
J/mf
(ASTM
D256A)

Products/Applications
Extrusion
Injection molding medium impact
Injection molding medium impact
High ow injection molding and thin-wall medium
impact
High ow injection molding and thin-wall medium
impact
Extrusion and injection molding high impact
Blush-resistant injection molding medium impact
Blush-resistant controlled rheology injection
molding medium impact
Blush-resistant injection molding high impact

308

PROPYLENE POLYMERS

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providing impact resistance well below 0 C. Copolymers containing high exible product. Mineral llers, such as talc or calcium carbonate, and other reinforcements such as glass ber or mica, increase the stiffness and heat-distortion
temperature. Some properties of mineral-lled iPP are given in Table 8. Filled
formulations based on impact copolymers (PP-EPR) are also common.

Catalysts for Polymerization

TiCl3 -Based Catalyst. Isotactic polypropylene was rst synthesized by
Natta in 1954 by employing a system consisting of TiCl4 and Al(C2 H5 )3 activator
(169174). It was based on Zieglers catalyst system (175), which was used for
the polymerization of ethylene. Only 3040% of the polypropylene produced by
Nattas catalyst had the typical characteristics of isotactic polypropylene; for example, it was insoluble in boiling heptane and had a melting point of about 165 C.
The remaining product was atactic with poor structural uniformity and a rubbery consistency. Natta quickly realized that the polymer isotacticity was directly
connected to the uniformity of the catalyst surface. Thus for the polymerization of
propylene, he employed solid crystalline TiCl3 (obtained by the reduction of TiCl4 )
(176) with Al(C2 H5 )2 Cl or Al(C2 H5 )3 and obtained a higher percentage of isotactic
product (see ZIEGLER-NATTA CATALYSTS).
The various TiCl3 structural forms, , , , and , were identied in subsequent studies (177); the -form, in combination with Al(C2 H5 )2 Cl, gave the best
results. The high polymer isotacticity (ca 90%) permitted a scaled-up industrial
process by Montecatini, which had supported Nattas research at the Politechnic
in Milan. This rst plant (and subsequent others) contained a large section for the
separation of the undesirable atactic fraction from the isotactic fraction and a section for the removal of catalyst residues that affected product quality. Substantial
progress was achieved in a short time (178,179).
Hercules discovered the role of hydrogen as a molecular weight regulator
(180). Esso improved performance by using AlCl3 in TiCl3 solid solution instead of
pure TiCl3 (181). Mitsubishi increased isotacticity to 9294% by adding an electron
donor, such as carboxylic acid ester, to the TiCl3 (182).
The treatment of the TiCl3 produced from the reaction between TiCl4 and
Al(C2 H5 )2 Cl, rst with the electron donor, diisoamyl ether, and then with TiCl4 ,
gave a highly stereospecic catalyst. This catalyst system was four to ve times
more active than -TiCl3 (183) and capable of producing a polymer with narrow
particle size distribution. This system can be referred to as the second-generation
catalyst (Table 9). However, the catalyst yield was still insufcient to reduce catalyst residues enough to eliminate the deashing step in the production process.
In the meantime it was established that only a small percentage of the titanium on the catalyst was actually active. The active titanium was located on the
lateral faces and edges, and along the crystal defects (184). This led to the realization that much of the catalyst mass acted as the support (185). Decisive progress
could be achieved by depositing the active Ti on a support whose residues, unlike
those of TiCl3 would not be detrimental to polymer properties.
MgCl2 -Supported Catalysts. Magnesium chloride, in the active form as
a support (186,187), increases catalyst yield and allows for the simplication of the

Table 8. Properties of Filled Homopolymera

Melt
ow,
(g/10
min)
(ASTM
D1238)
309

4
3
4
4
4
a Ref.

Tensile
strength,b
Mpac
(ASTM
D638)

Elongation,b
% (ASTM
D638)

Flexural
modulus
1%
secant,
Mpac
(ASTM
D790A)

34
83
31
29
30

12

4
4
7

1400
4500
1900f
2900f
1500f

168.
yield.
c To convert Mpa to psi, multiply by 145.
d To convert kPa to psi, multiply by 0.145.
e To convert J/m to ftlbf/in, divide by 53.38.
f Tangent method.
b At

Deection
tempeature
at 455
kPa,d C
(ASTM
D648)

Notched
Izod
Impact
at 23 C,
J/me
(ASTM
D256A)

Rockwell
hardness,
R
(ASTM
D785A)

Products/Applications

93
157
109
125
96

39
85
37
27
37

86

84
94
89

Injection molding homopolymer, general-purpose

20% glass lled homopolymer
20% talc lled homopolymer
40% talc lled homopolymer
20% calcium carbonate lled homopolymer

310

PROPYLENE POLYMERS

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Table 9. Different ZieglerNatta Catalyst GenerationsComposition, Performance,

Morphology and Process Requirements

Generation

Composition

Productivity,
kg of PP/g of
catalyst

-TiCl3 0.33AlCl3 +
AlEt2 Cl

2
3

-TiCl3 + AlEt2 Cl
35 (1015)
TiCl4 /ester/MgCl2 + 510 (1530)
AIR3 /ester
TiCl4 /diester/MgCl2 1025 (3060)
+ AlEt3 /silane
TiCl4 /diether/MgCl2 2535 (70120)
+ AlEt3

4
5

0.81.2

Isotactic Morphology
Process
index
control
requirements
9094

9599

Not possible Deashing

and atactic
removal
Possible
Deashing
Possible
Atactic
removal
Possible
None

9599

Possible

9497
9095

None

productivity: hexane slurry, 70 C, 0.7 MPa, 4 h, with hydrogen for molecular weight
control. Values in parentheses are polymerizations performed in liquid propylene at 70 C for 2 h with
hydrogen.
b Only possible with alkyl aluminum reduced TiCl to produce a catalyst within a 200300 m size.
3
a Polymerization

polymerization process in hydrocarbon slurry with the elimination of the costly

deashing step. This discovery and further improvements led to the development
of the superactive, third-generation catalysts (188193) (Table 9). Better yield,
higher stereospecicity, and morphology control resulted in simplied processes
in which the monomer is the polymerization medium.
Other catalyst systems that are usually soluble in the reaction medium are
of high scientic importance but not used industrially. Among these is the system
consisting of the product of the reaction of AlR2 Cl and Al2 R2 Cl4 with vanadium
compounds. This system is utilized in the production of syndiotactic polypropylene
at very low temperature (194,195).
Isotactic polypropylene has been obtained, although with very low yields,
from Ti and Zr benzyl compounds (196) and allylic derivatives (197).
Other highly active catalyst systems are based on single-site catalyst, for
example (-5 C5 H5 )2 M(CH3 )2 ; (M = Ti, Zr). These systems will be discussed in
more detail in the Homogeneous Catalyst section.

Heterogeneous Catalyst Preparation.

TiCl3 -Based Catalysts. First-generation catalysts are prepared by the reduction of TiCl4 with metallic aluminum in aromatic solvent between 100 and
200 C (198,199). A solid solution with the composition of AlCl3 3TiCl3 (200) is
formed. Milling converts the crystalline TiCl3 from the - to the -form, increasing its surface area and radically improving its performance (201); Al(C2 H5 )2 Cl is
the best activator. Hydrogen and Zn(C2 H5 )2 are the molecular weight regulators,
but diethyl zinc is rarely used. Typical performance for this type of catalyst is
reported in Table 9. Milling produces a catalyst, and thus a polymer, with broad
particle size distribution.
A second-generation catalyst (183) is prepared by reducing TiCl4 with
Al(C2 H5 )2 Cl in a hydrocarbon at 0 C. The 3TiCl3 AlCl3 product with surface area

Vol. 11

PROPYLENE POLYMERS

311

around 1 m2 /g thus obtained is washed at 35 C with diisoamyl ether to remove

most of the AlCl3 . The product is then treated with TiCl4 at 65 C and washed with
hydrocarbons. The catalyst has a high surface area (up to 150 m2 /g). In polymerization with Al(C2 H5 )2 Cl and hydrogen, it gives the average performance shown
in Table 9. The polymer has regular shaped, compact particles and narrow particle
size distribution, with an average diameter around 300400 m. Catalyst activity
is maintained by storage under refrigeration.
MgCl2 -Supported Catalysts. The scientic and patent literature reports
several methods for the preparation of the MgCl2 -supported catalysts of third and
superactive third generations. They can be classied as follows:
(1) Catalysts obtained by milling mixtures of anhydrous MgCl2 with an electron
donor and a titanium compound (186,187)
(2) Catalysts obtained by milling anhydrous MgCl2 with an electron donor and
treated with a titanium compound (TiCl4 ) above 80 C, followed by washing
with hydrocarbons (188192)
(3) Catalysts obtained by treatment of active MgCl2 with an electron donor
and a titanium compound (TiCl4 ) under conditions similar to those of the
previous case (202)
The second method gives the average results reported in Table 9 with regard
to third-generation catalysts. In practice, anhydrous MgCl2 and an aromatic ester,
usually ethyl benzoate (EB) in molar ratios between 2 and 15, are shaken in a
vibrating mill containing steel spheres for 20100 h. The MgCl2 is activated; that
is, it is converted from the crystalline ordered form to the disordered -form while
the crystallite size is reduced.
The product is treated twice with an excess of TiCl4 between 80 and 130 C,
washed repeatedly with hydrocarbons, and dried. During the treatment with
TiCl4 , the base is partially extracted, and TiCl4 enters the support. The nal
composition of the solid includes 0.53.0 wt% Ti and 515% EB; the remainder is
MgCl2 . The surface area is in excess of 100 m2 /g. The active or -form of MgCl2 resembles the -form of TiCl3 (203). It can also be obtained by direct contact of anhydrous MgCl2 with Lewis base or by chlorination of magnesium organic compounds
(188192). The degree of activation can be determined by X-ray diffraction (203),
where the passage from to gives rise to a widening and lowering of the diffraction peaks. The active form, because of the corners, edges, and surface defects of
the crystallites, binds the titanium compound strongly, and repeated washing or
treatment under vacuum cannot remove it. This strong binding is attributed to
the closeness of the Mg and Ti ionic radii (204) and to the similarity among the
crystallographic forms of their halogens. The Ti atoms located in exposed sites
give rise to polymerization active centers (205208). Magnesium chloride may
easily interact with electron donors, probably affecting the stereospecicity of the
active site. It can be easily transformed into particles with controlled morphology because of the low melting point of its adducts with alcohols or water. These
catalysts are used with aluminum trialkyl alone or in blends with chlorinated aluminum alkyls and with a second electron donor, which can be equal to or different
from that contained in the solid catalyst.

312

PROPYLENE POLYMERS

Vol. 11

Heterogeneous Catalyst Evaluation. To evaluate a catalyst system, the

following characteristics must be known: yield or productivity, which is the amount
of polymer produced per unit of total catalyst or single component; the polymerization kinetics, or yield development with time; stereospecicity; sensitivity to
the molecular weight regulator; the molecular weight distribution of the polymer
produced; the microtacticity of the resulting polymer; ability to copolymerize; and
the nal polymer morphology.
To forecast the behavior of a catalyst system in an industrial continuous
polymerization, these characteristics should be determined within a wide range of
conditions; eg, temperature, concentration, and ratios of the various components
(activator, external donor, solid catalyst, etc). A laboratory batch-scale test can
provide most of this information. A small, simple reactor suitable for these studies
is shown in Figure 8. The polymerization can be carried out in a hydrocarbon or
liquid propylene. In some cases the polymerization test can be performed in the
gas phase, provided the reactor is prepared with a suitable heat transfer and
catalyst dispersing bed (eg, a salt bed).
The stainless steel reactor is provided with a jacket for temperature control
in the range 0.5 C using a steam and chilled water mixture. The reactor contents are agitated by a magnetic stirrer (500900 rpm). The consumption of the
propylene is followed by weighing the vessel from time to time or through gas ow
meters.
A test using hexane as diluent is the simplest to perform because it does
not require the safety measures required for tests in liquid propylene. It can be
carried out as follows.

Fig. 8. Lab-scale polymerization reactor.

Vol. 11

PROPYLENE POLYMERS

313

The reactor is kept under nitrogen at 4050 C to exclude oxygen and moisture. Anhydrous, deaerated hexane is introduced followed by a xed amount of
catalyst. The reactor is closed and heated to 6070 C, and hydrogen and propylene are fed at the desired concentrations. These feeds are maintained for a certain
time. Data on the polymerization kinetics are obtained from the mass of propylene
fed over time. At the end of the test the temperature is reduced, the reactor degassed, and the slurry (hexane/polypropylene) discharged from the reactor (either
through a dip tube or a bottom valve). The polymer is separated from the hexane by
ltration or by evaporation. The polymer is dried at 60 C under nitrogen, weighed,
and analyzed.
Typical graphs follow which represent the performance of a superactive,
third-generation catalyst system as a function of processing variables. The activity is expressed as kilograms polymer per gram catalyst, and the isotacticity
as polymer percentage residue from a boiling heptane extraction in a modied
Soxhlet extractor for 12 h.
Figure 9 shows the trend of activity for polymerizations in hexane with a
propylene concentration of 14% at 70 C; Figure 10 shows the isotactic index.
Polymerization temperature, as reported in Figure 11, inuences performance; an increase from 50 to 80 C increases both activity and isotacticity.
Isotacticity should be between 94 and 98% to meet various application requirements. The ratio between aluminum and electron donor controls stereospecicity. At very high levels of electron donor the activity will be reduced, as shown
in Figure 12 (209).
The aluminum compound alkylates the transition metal and can act as a
transfer agent. It also removes impurities from the reaction medium (eg, water,
CO2 , alcohols), thereby avoiding catalyst poisoning. In addition, aluminum alkyl
reduces the transition metal to lower valence, thus affecting its activity (210).
In the case of supported catalysts, aluminum alkyl plays a fundamental role by
complexing the electron donors (204).

Fig. 9. Activity vs polymerization time.

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Fig. 10. Isotactic index vs polymerization time.

Fig. 11. Activity and isotactic index vs polymerization temperature.

Polymerization Reaction Mechanisms

The rate Rp of the primary propagation step of monomer to polymer in Ziegler
Natta catalysis is represented by
Rp = kp [C ][M]
where kp is the propagation constant, [C ] the concentration of active sites, and
[M] the monomer concentration.

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Fig. 12. Activity and isotactic index vs Al:donor ratio.

The global polymerization rate changes with time. A period of increasing

rate is usually followed by a decline and eventually by a stationary state. The
rate decay is often attributed to the change in concentration of active sites in
the context of the above noted expression. The initial increase may be due to the
progressive activation of new active centers. The deactivation, particularly evident
in supported catalysts (211,212), is attributed to variations in both number and
chemical nature of the centers (213).
Global polymerization rate and rate of primary propagation are affected by
the catalyst system and polymerization conditions (203,214). Effects are due to
the chemical and physical structure of the catalyst as well as to the nature of the
activator. Important parameters include the ratio between catalyst and activator,
and their concentrations, hydrogen concentration, temperature, stirring rate, and
type and amount of Lewis base. The effects vary with the polymerization medium;
ie, diluent or the monomer in liquid or gas phase (215218).
The complexity of the catalyst systems and their heterogeneous nature make
an accurate analysis of the parameters associated with the primary propagation
step difcult. This is one reason why literature analyses are rarely in agreement;
also, the data are obtained by methods and under conditions that are rarely comparable. A typical example is the determination of the concentration of the active
sites and the propagation constant, which can be carried out by various methods (chemical, radiochemical) that are not completely reliable. Nonetheless the
parameters are valuable in determining catalyst potential and performance.
The same uncertainty is involved in the determination of the activation energy of the propagation reaction and the average lifetime of the polymer chain.
A value of 23 kJ/mol (5.5 kcal/mol) for TiCl3 -based catalysts is reported for the
former (219). For the latter, values of 360600 s (220) and 160 s (219) for TiCl3 based catalysts are reported at 70 C and 5 s (221) for MgCl2 -supported catalysts
at 45 C.
A short time after the discovery of ZieglerNatta catalysts, it was suggested
(222,223) that chain propagation occurred by monomer insertion into a Ticarbon

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bond of the catalyst. This bond was considered to be polarized, with a weak negative charge on the carbon atom; this hypothesis is still widely supported today.
It was conrmed by IR analysis of chain terminal groups (224) as well as by 13 C
enriched aluminum alkyls (225).
In an attempt to provide a model to explain the growth of the polymer chain
satisfactorily, several hypotheses have been suggested. In Boors book on Ziegler
Natta catalysis (179), he exhaustively reviewed the literature and addressed four
mechanisms for chain growth. The four mechanisms are based on the description
of the center where chain growth takes place:
(1)
(2)
(3)
(4)

transition metalcarbon bond,

activator metalcarbon bond,
bound radical center, and
bound anion center.

Of these four, the majority of the research tends to support the transition
metalcarbon center model, as the mechanistic scheme of choice. Using a homogeneous catalyst (Cp2 TiEt2 ) as a model, Breslow and Newburg proposed that polymerization growth occurred at the Ti C center. Somewhat later, Cossee extended
this concept into a more elaborate mechanism for supported catalysts, which he
substantiated with molecular orbital calculations (see Ref. 179, Chapt. 13).
According to this widely accepted model (226230) for the surface site and
surface coordination environment, the active site is a titanium atom with octahedral shape and a vacant position (the other positions being occupied by an alkyl
group derived from the alkylation by the aluminum alkyl and the remaining chloride atoms). In total the active site is made up of four ligands, which, in the case
of TiCl3 , are chlorine atoms, the alkyl group, and the vacant site.

Monomer insertion occurs through a rst step of monomer coordination to

the transition metal, with formation of a -complex, subsequent weakening of

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the Ti C bond, and nally insertion of the monomer coordinated between the
transition metal and the C atom. Because the two positions are not equivalent
in the crystal lattice of the catalyst, the vacancy and the growing chain exchange
positions. These phases are repeated at the insertion of each monomer unit. On the
basis of molecular orbital theory, a semiquantitative interpretation of the mechanism was provided by assuming weakening of the metalcarbon bond during
olen complexation in the case of metal ions with 03 d-electrons (as in Ti, V, Cr),
and with more difculty when the number of d-electrons is greater. This mechanism is called monometallic; it requires only the participation of the transition
metal, attributing to the aluminum compound the role of forming the active center by alkylating the titanium atom. The aluminum compound is also involved, as
demonstrated by the different effects that various aluminum alkyls have on the
performance of these catalyst systems.
Some researchers believe that the active metal (aluminum) directly participates in directing of the incoming monomer, in which case this system would be
considered a bi metallic site. However, Boor makes a convincing argument that because of the size of the polypropylene helix, there is no room at the active site for the
aluminum to participate. The titanium site occupies roughly 0.16 nm2 (diameter
0.45 nm) and the cross-sectional area of a polypropylene helix is about 0.35 nm2
(diameter 0.7 nm). This would eliminate the titanium and aluminum from sharing a common chloride bridge and thus preclude aluminum from directly participating in directing the incoming monomer (179). It has been suggested that the
effect the different aluminum alkyls have on polymer microstructure and molecular weight is due to the way in which the alkyl aluminum sets up the titanium
chloride surface. These differences in polymer microtacticity and molecular weight
could be due to the fact that the activator may be generating different isotactic
sites.
The basic concept of monomer insertion has now been discussed and for the
polymerization of ethylene this simple description of a monometallic, transition
metalcarbon centered active site would be sufcient to describe the polymerization. However, with -olens the matter of stereo- and regio-chemistry must be
addressed and will be done in the next section.
Stereo- and Regiochemistry of Monomer Insertion. For substituted
-olens a number of issues concerning monomer coordination/insertion must be
considered. The way in which the monomer inserts itself into the polymer chain
determines the microstructure of the polymer and subsequently the properties.
Does the methyl group on the propylene end up towards the chain or away? What
is the position of the methyl group on the propylene molecule with respect to coordination site of the metal and the polymer chain, cis versus trans? The way
in which the propylene molecule may be inserted in the polymer chain by various mechanisms can give rise to complex phenomena of structural and steric
isomerism.
Two possible regio-insertion mechanisms for -olens existprimary and
secondary. In a primary insertion the unsubstituted end (methylene group) of the
monomer attaches to titanium center. This is also known as a 1,2-insertion. In a
secondary insertion the substituted end of the monomer attaches the titanium.
This is also called a 2,1-insertion.

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The experimental evidence indicates that for the production of isotactic

polypropylene the primary insertion mechanism is predominant. This is substantiated via end group analysis by the presence of isopropyl groups as the end groups
after chain transfer by hydrogen. The regioselectivity of ZieglerNatta catalysts is
very high as have been proved by NMR analyses (231,232). Syndiotactic polypropylene can be prepared by the low temperature polymerization of propylene using a
vanadium catalyst. In this case the secondary insertion mechanism is operative
(233,234).

For stereoregular insertion there are two modes to considercis insertion

and trans insertion. For both isotactic and syndiotactic production, the cis mechanism has been determined to be in operation. This was established by polymerizing
with cis-, and trans-1-deuteriopropylene or related monomers. The expected stereochemistry was demonstrated when deuteriopropylene was polymerized. The cis
monomers produce erythro monomer units whereas the trans monomer yields the
threo units when cis- and trans-1-d-propylene is polymerized. In some cases the
nomenclature appearing in the literature can be confusing and contradictory, but
all indicate cis insertion. To be specic, as dened below, stereochemical structures from cis and trans addition to the double bond of cis-(1-d1 ) and trans-(1-d1 )propylene to isotactic polypropylene are as follows (229):

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Two potential mechanisms have been proposed as governing factors regulating the stereochemistry of the isotactic insertion, the rst being the asymmetric structure of the active site (enantiomeric site control) and the second being
the asymmetric carbon atom of the last chain-inserted monomer unit (chain end
control). It has been proved experimentally that the regulating factor is the active center (enantiomeric site control) because the steric order is transferred also
through ethylene units and because an occasional error is not perpetuated in the
chains (231,232). This mechanism is valid for ZieglerNatta catalysts and many
(if not most) homogeneous metallocene catalysts. In addition it has been shown
(235240) how, in the polymerization of racemic -olens, a mixture of optically
active polymer can be obtained with an asymmetric catalyst.

Examination of the crystalline structure of the catalyst components reveals

the asymmetric structure of the active center. In TiCl3 six chlorine atoms at the
vertices of an octahedron surround each titanium atom. These six chlorine atoms
are then chelated, by pairs, to three other titanium atoms. This creates two enantiomorphic structures.

The next section will discuss some of the concepts associated with models for
the catalytic sites.

ZieglerNatta Active Site Models

An important characteristic of a polymerization catalyst is its morphology or structural architecture. Titanium chloride exhibits four different crystalline modications: , , and forms depending upon the method of preparation. In each

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case the titanium atom is octahedrally coordinated, except at various defects and
edges. The violet -form, and the and forms consist of regular stacking of
Cl Ti Cl layers containing titanium atoms between two layers of chloride ions.
The -TiCl3 form, which will be discussed, is hexagonally close packed.
Stereospecic behavior of the catalyst site is related to the chirality of the
surface sites of the solid TiCl3 . Models by Corradini can explain a number of
observationsthe type of tacticity errors along a predominantly isotactic chain,
stereospecicity of the initiation reaction, and the maintenance of isotacticity after the insertion of ethylene monomer in the chain (241). Furthermore, since violet
TiCl3 and MgCl2 solid-state crystal structures are similar, Corradinis model relates well to both TiCl3 and MgCl2 -supported catalysts.
The structure of titanium trichloride and other ZieglerNatta catalysts consisting of transition metal halides (VCl3 , CrCl3 , etc) is comprised of layers of closepacked chlorine atoms. The crystalline modications are based on the different
ways in which the layers are stacked on top of one another. Within each layer
the metal atoms reside in an ordered arrangement. The metal atoms occupy two
thirds of the octahedral positions. The adjacent metal atoms, which are bridged
by two chlorine atoms, have opposite chirality. The chirality of these metal atoms
is designated  and
according to the International Union of Pure and Applied
Chemistry (IUPAC) nomenclature (242). In the MgCl2 structure there are no vacancies in the lattice and every octahedral position is occupied by a magnesium
atom; however, it can be seen that the gross structures of TiCl3 and MgCl2 are
similar. This similarity in structure between TiCl3 and MgCl2 is what makes magnesium chloride a suitable substrate for the deposition of titanium chloride to form
active sites. It was determined early on that only a small portion of the titanium on
TiCl3 catalysts was active; the rest was essentially acting as a support. The bulk
of the titanium chloride was the culprit in causing polymer instability and degradation problems. When using MgCl2 as a support the yield of polymer per weight
of catalyst is much greater. Along with the fact that the magnesium chloride is
practically inert, this produced a polymer that was inherently more stable.
A diagram of the TiCl3 structure of the (110) cut and the (100) cut of MgCl2
is shown in Figure 13; the chloride atoms are omitted for clarity.
Magnesium chloride can be treated either chemically or physically (ball
milling) to achieve activation. Activated MgCl2 has a very disordered structure,
which consists of very small lamellae. In the bulk, magnesium atoms are coordinated to six chlorine atoms, but at the lateral edges or cleaved surfaces the
coordination is with 4 or 5 chorine atoms. These lateral cuts correspond to the
(110) and (100) faces respectively for magnesium chloride. Upon treatment of activated MgCl2 with TiCl4 , the bridged dinuclear Ti2 Cl8 species coordinate on the
(100) surface while the single TiCl4 species usually prefer the (110) faces. Treatment of the catalyst by aluminum alkyls will reduce the Ti2 Cl8 to Ti2 Cl6 species
and alkylate the titanium. This will generate both TiCl3 and Ti2 Cl6 species on the
MgCl2 support. The placement of these Ti2 Cl6 units on the (100) lateral surface of
MgCl2 produces sites very similar to those on the (110) surface of TiCl3 catalysts.
These Ti2 Cl6 sites are chiral and stereospecic. Coordination of the TiCl4 species
on the (110) faces and reduction by aluminum alkyls produce TiCl3 sites, which
lack chirality and are nonstereospecic producing sites for propylene polymerization. In Figure 14, is shown both the TiCl3 catalyst and MgCl2 /TiCl4 catalyst after

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Fig. 13. Comparison of the structures of -TiCl3 and MgCl2 .

reduction with AlR3 . Now with the basics of the active centers and structures
described, the details of the polymerization mechanism can be discussed.
As mentioned previously, a two-stage reaction mechanism for the polymerization of propylene was proposed which consists of a coordination stage of the
olen then followed by an insertion step of the monomer into the Tipolymer
bond. Although this picture (Fig. 15) reveals the basic mechanism of monomer
coordination and then insertion, it does not provide any insight into the mechanism for stereocontrol of the propylene monomer. This is addressed by chirality
considerations.

Fig. 14. Crystal structures of -TiCl3 and MgCl2 with Ti2 Cl6 clusters. Chlorine atoms are
shown at the catalyst sites, and substrate chlorine atoms are omitted for clarity.

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Fig. 15. Propylene coordination to titanium and then insertion of propylene into the
Tipolymer bond.

As discussed previously the active sites on TiCl3 -based catalysts or MgCl2 supported catalysts are chiral. In all, there are three elements of chirality that are
considered with respect to the polymerization of -olens and stereospecicity of
the polymer:
(1) or chirality of the titanium atoms
(2) The si or re chirality of the coordinated propylene monomer
(3) The chirality of the tertiary carbon atoms of the growing polymer chain
For this discussion the bridged dimers of Ti2 Cl6 on the lateral face of a MgCl2
crystal will be considered. If Figure 16 (below) is studied in detail, it can be seen
that at one of titanium atoms of the Ti2 Cl6 cluster there are two positions that
are available to the growing polymer chain and the coordinating monomer. One
position can be considered outside or away from the bulk of the crystal and the
other can be considered inside, or towards the bulk of the crystal lattice. These two
positions are not sterically equivalent. Through computer modeling calculations,
Corradini and co-workers demonstrated that the most favorable energy position
for the growing chain was at the inside position (241).
If the most favorable energetic position for the chain is at the inward position,
then the monomer must occupy the outside location. For the  titanium site, the si
outward coordination of propylene is favored (re for the outward
titanium site).
In this model the production of stereospecic polypropylene can be explained.
For syndiotactic propagation it was proved that the steric control of the insertion comes from the last inserted monomer unit, whose hindrance affects the

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Fig. 16. Inward and outward positions available for occupation by the monomer and
polymer chain.

insertion of the subsequent unit in such a way as to prevent a monomer molecule

with the same conguration of the previous molecule from entering (243,244).
Recall that syndiotactic polymerization from ZieglerNatta vanadium catalysts
differs from this isotactic polymerization monomer insertion. For the vanadium
syndiotactic catalysts secondary or 2,1-insertion is operative (233,234). More recently developed homogeneous syndiotactic catalysts follow 1,2-insertion.
Summarizing, isotactic and syndiotactic propagation highlights the catalyst site as the entity controlling stereoregularity for iPP and the last monomer
unit of growing chain for syndiotactic propagation with vanadium catalysts. The
monomer insertion type is primary (1,2) for isotactic and secondary (2,1) for this
latter syndiotactic catalyst.

Electron Donors
There are two classications of electron donors, internal and external. Electron
donors are thus named for their ability to act as Lewis bases and donate electrons
to Lewis acid sites. For the TiCl3 type catalyst, the electron donors are traditionally referred to as just donors and are generally amines, esters, ethers, alcohols,
etc. Their roles range from modifying the catalyst site and structure of the TiCl3
substrate to complexing with the alkyl aluminum either during catalyst preparation or catalyst activation.
For MgCl2 -supported catalysts (the third- and fourth-generation types; see
Table 9 the electron donors are classied as internal and external based on their
sequence of addition during catalyst preparation or during activation, respectively.
For the preparation of the MgCl2 -supported catalyst an electron donor is added

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during the process of adding the TiCl4 (titanation of the support) to the activated
MgCl2 -support; this is referred to as the internal donor. At the stage of activation of the MgCl2 -supported catalyst, another donor is added during the addition
of the alkyl aluminum; this donor is referred to as the external donor. For the
third-generation MgCl2 -supported catalyst, the internal donors are usually phthalates and the external donors are alkyl alkoxy silanes. For the fth-generation
type catalysts, the internal donors are diethers and the external donor (alkyl
alkoxy silane) may or may not be used. In most cases electron donors are used to
increase the activity and stereospecicity of the catalyst system.
Donors work in a variety of ways and the roles of both internal and external
donors as they relate to the MgCl2 -supported catalysts will be discussed in this
section. As mentioned previously, MgCl2 can be activated through mechanical or
chemical means. The process of activating magnesium chloride through mechanical means can be achieved by ball milling. This process usually involves co-milling
the magnesium chloride with a Lewis base (233). The preparation of the catalyst
is followed by treatment of the activated magnesium chloride with TiCl4 and heat.
The subsequent treatment of the MgCl2 /internal donor support with TiCl4 usually
removes some to the internal donor. In other cases the activated MgCl2 -support
can be treated with TiCl4 and the Lewis base at the same time, and then given
a heat treatment. The internal donor helps structurally stabilize the activated
magnesium chloride, prepare sites for the TiCl4 , and possibly block certain sites
on the MgCl2 surface, thus making them unavailable for titanium chloride.
Whereas third-generation ZieglerNatta catalysts use an ester (ethyl benzoate, EB) as internal donors and another ester as the external donor (methyl
para-toluate, MPT), the fourth-generation catalysts use a phthalate (usually diiso-butylphthalate, DIBP) as the internal donor and an alkyl alkoxy silane (eg
phenyl triethoxy silane, PES) as an external donor (233). In both cases the internal and external donors play similar roles. The internal donors stabilize the MgCl2
support and set up positions for the TiCl4 complex. The purpose of employing an
external donor in both the third- and fourth-generation catalyst systems is that
without them, the stereospecicity of the catalyst would be very poor for the polymerization of propylene. This is due to the fact that activation of the catalyst with
the alkyl aluminum extracts a portion of the internal donor out of the catalyst.
The external donor is added during the activation of the catalyst for the purpose
of occupying the site left vacant by the extracted internal donor (233).
From the discovery of the high yield MgCl2 -supported catalysts it was apparent that the presence of both an internal and external donor was a necessary condition for a highly active, highly stereospecic catalyst. Soon after, it was
learned that an interrelationship existed between the two donors and, furthermore, specic donor pairs gave optimum results. However, with the advent of the
fth-generation catalysts, those employing diethers, there was no need for the addition of an external silane donor (234). These catalysts, MgCl2 /TiCl4 /diether, did
not lose the internal donor during activation with the alkyl aluminum and consequently maintained relatively good stereocontrol and excellent activities (2 to 3
times that of the conventional MgCl2 -supported/phthalate catalysts) (245,246)
(see Table 9). Interestingly enough, these diether donors can also be used as external donors in the more traditional MgCl2 -supported/phthalate/TiCl4 catalyst
systems and they produce the same type of homopolymer. This supports the theory that there is a phthalate/external donor exchange during activation where

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the external donor (diether) occupies the site left vacant by the phthalate, very
similar to the phthalate/alkoxy silane exchange. In general the following model
best describes the interactions between the internal and external donors with the
catalyst and activator (246,247):
(1)

(2)

(3)

(4)

(5)
As previously mentioned, the alkyl activator will extract internal donor from the
catalyst; therefore equilibrium 1 is always present even in the absence of an external donor. Depending upon the location of the titanium site on the magnesium chloride support, the free site (Cat-
) could be isospecic or aspecic. Equilibrium 2
is also present because of the propensity of the external donor and AlR3 to form
acid/base adducts. These EDAlR3 adducts may also form exchange products (248).
In fact, these exchange products are important because they reduce the concentration of free external donor present in the system, which also acts as a poison. In
the presence of excess aluminum, there should be very little free external donor
present in the system; therefore equilibrium 3, (the interaction of catalyst with
free external donor) can be neglected. For the external donor to interact with
the free titanium site there are two possibilitiesthrough the EDAlR3 complex
(equilibrium 4) and through the EDAlR3 complex initially as a carrier for the
ED (equilibrium 5). In equilibrium 5, the EDAlR3 complex releases the ED to
the vacant titanium site. Experimental results indicate equilibrium 5 as the most
likely case. The alkyl aluminum activates the titanium and removes the internal donor but does not participate in the actual stereochemical regulation of the
polymerization of propylene (246).
To recap, there are two types of donors, internal and external. For the thirdgeneration catalysts the internal/external pair is an ester/ester pair, while for
the fourth-generation it is the phthalate/alkoxy silane pair. The fth-generation
ZieglerNatta catalysts are comprised of an internal donor, which is a diether
compound and may be used with or without the additional external donor
(see Table 9).
There has been a large effort towards elucidating the roles of the external
donor in the polymerization of propylene. Some of this work has centered on the

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structural considerations of the external donor. Since the MgCl2 /TiCl4 /phthalate
alkoxy silane/AlR3 catalyst system is the most widely used commercial catalyst
system for polymerization of propylene, the focus in the next section will be on the
alkoxy silane as the external donor.
Structural Considerations of Electron Donors. The most effective
alkoxy silanes used in the polymerization of propylene give the greatest activity
along with the highest selectivity. These types of silanes are of the general formula R1 R2 Si(OR)2 and R1 Si(OR)3 , with R = methoxy or ethoxy (any larger alkoxy
group is ineffective). Early on, PhSi(OEt)3 was used; however, the more effective
silanes for catalyst performance are those that contain methoxy groups (R = OMe).
Interestingly enough, silanes with only one alkoxy group were poor performers,
producing polypropylene with low isotacticity. The best activity/selectivity balance
was found for silanes having two methoxy groups and two alkyl groups (R1 and R2 )
that are relatively largein other words, sterically bulky. The importance of steric
volume was investigated by Okano and co-workers (249). They correlated silane
molecular volume and electron density (calculated by molecular modeling) with
polymerization performance (activity) and stereocontrol (isotactic index). In their
study they found a straight-line correlation with silane volume and isotacticity.
onen (250) found a decrease in atactic polymer forBoth Okanos group and Hark
mation with an increase in electron density.
In addition to affecting polymer stereoregularity and catalyst activity, silane
donors inuence other aspects of propylene polymerization. It was also found
that external silane donors inuenced molecular weight of the polymer via the
use of hydrogen as a chain-transfer agent. When using hydrogen to decrease the
molecular weight of the polymer, there was also an increase in activity when using an external alkoxy silane with the MgCl2 /TiCl4 /phthalate ester catalyst system (251254). While hydrogen is used as a molecular weight control agent, this
level of control varies from external donor to external donor. In some cases, under the same hydrogen charge, two different donors will give polypropylene with
two very different molecular weights (255). These differences between donors in
molecular weight control are not unlike the differences observed in stereocontrol.
Some donors are better at stereocontrol than others. The general observation is
that donors with good stereocontrol or high selectivity (usually those containing
bulky hydrocarbon groups) are usually poor at effectively using hydrogen to lower
the molecular weight of the polymer. Donors with poor regio- or stereocontrol
exhibit good hydrogen response. Chadwick and co-workers have explained this
phenomenon by the process of chain transfer after a regioirregular insertion of
propylene (256). With a 2,1-insertion it is harder for the next propylene unit to
insert into the Ti CH(CH3 )CH2 polymer bond; however, there is a probability
of hydrogen inserting to affect a chain transfer. Therefore those donors with low
regio-control permit more 2,1-insertions, thus making chain transfer with hydrogen easier. Donors with good regio- control make far fewer 2,1-insertions, thus
denying an easy path and an opportunity towards chain transfer with hydrogen.

Molecular Weight and Molecular Weight Distribution Effects of

Electron Donors. The production of broad molecular weight distributed
polypropylene is a function of the multiplicity of active centers, which differ in
stereo- and regiospecicity, and the propagation rate. Lewis bases in general, and
external alkoxy silane donors in particular can inuence the molecular weight

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distribution of polypropylene by associating with these multiple active centers

(245,257,258). The regio- and stereoselectivity of the external donors affects the
molecular weight distribution of the polymer indirectly. Normally the atactic fraction of polypropylene has a lower molecular weight. This is in part due to regioirregular insertions of the monomer, which in turn leads to the easier pathway of hydrogen complexation and subsequent chain transfer (259). It has been
shown that the different fractions of homopolypropylene separated by temperature rising elution fractionation (TREF) not only differ in microtacticity but also by
molecular weight (245). For the MgCl2 /TiCl4 /diether based catalyst, Chadwick and
co-workers found that the higher temperature eluting fractions also had higher
molecular weights. Not unexpectedly, each fraction from TREF exhibited a narrow
molecular weight distribution (259).
Microtacticity Considerations. In the early days of ZieglerNatta polymerization of propylene, two concerns were activity of the catalyst and the stereospecicity of the polymer. Stereospecicity or stereoregularity of the polymer was
measured by the amount of insolubles produced versus the amount of solubles.
However, another important feature affecting the performance of polypropylene
is the microtacticity of the polymer chain. Nowadays, with the aid of TREF and
13
C NMR spectroscopy, the overall stereospecicity of polypropylene can be further dened by observing stereoirregular and regioirregular insertions. The type
and quantity of these disruptions in the chain lead to differences in the physical
properties and processing performances.
Chadwick and co-workers demonstrated that the quantities of the three major fractions derived from TREF vary with different donors (256). The fraction of
polymer that elutes from 26 to 95 C, normally referred to as the stereoblock fraction, can vary from as little as 4% up to 21% by weight of the total polypropylene
sample (260). The differences in homopolymer made with two different donors can
be seen by looking at the mmmm pentads, via 13 C NMR spectroscopy, of the TREF
fraction eluting from 96 to 125 C.
In summary, donors, both internal and external (alkoxy silanes and diethers),
affect catalyst performance and polypropylene properties in the following ways:
(1) The internal donors restrict the placement of titanium on the (110) face of
MgCl2 .
(2) The internal donors shift the equilibrium between the aspecic monomeric
species (TiCl3 ) to the stereospecic dimeric species (Ti2 Cl6 ) on the (100) face
of the MgCl2 .
(3) The external donors transform nonstereospecic sites into isospecic sites
by blocking open coordination sites near the titanium active centers.
(4) External donors control the path of the incoming monomer to varying degrees:
a. Little control produces stereo- and regioirregularities that result in microtacticity changes; this in turn affects crystallinity and thus the solubles levels.
b. Lack of monomer insertion control also affects regioirregular insertions
(2,1-insertions), which leads to chain transfer by hydrogen and lower
molecular weight.

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Metallocenes
Metallocene catalysts for the polymerizations of olens have been known since
early 1957 when Natta and co-workers rst reacted triethyl aluminum (AlEt3 )
and bis(cyclopentadienyl) titanium dichloride (5 -C5 H5 )2 TiCl2 to form a complex
that polymerized ethylene. The structure of this complex was described and the
polymerization results reported. With ethylene they reported to have made 7 g of
crystalline polyethylene in about 8 h at 95 C with 40 atm ethylene pressure in
n-heptane. Later in the same year, Breslow and co-workers repeated Nattas experiments. They found that the blue complex described by Natta was a somewhat poor
catalyst (in agreement with Nattas ndings), but discovered that small amounts
of oxygen in the ethylene boosted polymerization activity. When compared to the
heterogeneous ZieglerNatta catalyst system, these metallocene catalysts were
poor with respect to polymerization activity. They were used essentially for mechanistic studies because of their simplicity and ease of structure elucidation.
In 1975 Kaminsky found that a slight amount of water added to a mixture of biscyclopentadienyl titanium dimethyl and trimethyl aluminum rapidly
polymerized ethylene. Eventually it was determined that the addition of water
produced methylaluminoxane (MAO), which was responsible for the boost in activity (261). Although these Cp2 MX2 /MAO catalyst systems rapidly polymerized
ethylene and copolymerized other monomers with ethylene, they were less effective for the polymerization of propylene. There were several critical shortcomings with these early metallocene catalysts toward the polymerization of propylene: low activity, poor stereospecicity, and low molecular weight polypropylene
production.
Because these metallocene catalysts are discrete, single molecules, their
structures can easily be determined by X-ray crystallography. This allows the
catalyst chemist to begin the process of relating the structure of the metallocene
catalyst to polymer properties (molecular weight, stereoregularity, stereospecicity, etc) and polymerization activity. This ability to relate catalyst structure to
polymer properties allows the process of elucidating polymerization mechanisms
and designing catalysts to tailor make polymers and copolymers. This is a big
advantage over the traditional ZieglerNatta catalysts, which contain multiple
sites (see METALLOCENES; SINGLE-SITE CATALYSTS).
General Description of Structures. A brief description of metallocene
catalyst structures is necessary before going any further in discussions concerning
these systems. In their most basic form these metallocenes consist of a Group
IV metal (M= Ti, Zr, Hf), two -bonded cyclopentadienyl rings, and two sigmabonded groups (these rings are also referred to as carbocyclic -ligands while all
the groups attached to the metal are generally referred to as ligands). Because of
the nature of the -bonding between the metal atom and the carbocyclic -ligands,
there is free rotation of these ring groups about their metal-to-ring centroid axes.
This free rotation makes these metallocenes nonstereorigid and produces atactic
polypropylene.
A bridged metallocene contains a linking unit (usually CH2 , CH2 CH2 , or
SiR2 ) between the two carbocyclic ligands. These bridged metallocenes are stereorigid, but will not necessarily produce stereospecic polypropylene.

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Furthermore, these bridged metallocenes can become more complicated

structurally with more substitutions on the carbocyclic -ligands. In fact,
the more complicated bridged metallocenes are of commercial interest because they provide for the production of isotactic and syndiotactic forms
of polypropylene at high molecular weights. Because of the carbocyclic
-ligands complexity, catalyst stereochemistry will be addressed in the next few
paragraphs.
Bridged metallocenes can be further classied based on their stereochemistry. Using an ethylene-bridged bis-indenyl metallocene (CH2 CH2 [Ind]2 MX2 ) as
an example, one can follow the spatial relationships between the ligands and
their effects on monomer insertion mechanisms and polymer properties. The
CH2 CH2 [Ind]2 MX2 metallocene can exist in two forms, mesomeric and racemic
(meso and rac). The meso-CH2 CH2 [Ind]2 MX2 catalyst has a mirror plane and
is nonstereospecic in the polymerization of propylene; it is designated as
Cs -symmetric. The rac-CH2 CH2 [Ind]2 MX2 catalyst has a nonsuperimposable mirror image and, to a certain degree, each enantiomer is a stereospecic catalyst site;
it is labeled as C2 -symmetric.

Finally, two other structural types of metallocenes need to be mentioned. One

type consists of carbocyclic -ligands, which are not identical but each possessing
a plane of symmetry (orthogonal to the ring plane). These types of metallocenes
are labeled as Cs -symmetric. The other type of metallocene contains two nonidentical carbocyclic ligands, one symmetrical and one asymmetrical. These types of

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metallocenes are labeled as C1 -symmetric.

Implications of Metallocene Catalyst Structure on Polypropylene

Structure. The previous section gave a brief description of the various types
of metallocenes. In this section a general relationship between metallocene structure and type of polypropylene produced will be made. It is important to note that
these are generalizations. While the stereochemistry of the metallocene plays an
important role in mechanism of monomer insertion and ultimately the stereo- and
regiospecicity of the polymer, the substituents and location of the substituents
on the carbocyclic -ligands also effect the microstructure of the polymer.
In general, metallocenes that are either bridged or nonbridged and posses C2v
symmetry (eg, Cp2 TiCl2 or Me2 Si[uorenyl]2 ZrCl2 ) will produce atactic polypropylene. This is because these types of catalysts have low stereocontrol. The only
stereocontrol mechanism operating in these systems is chain end control from the
polymer. Consequently the polymer is predominately atactic at normal polymerization temperatures. In fact, these metallocenes are the best source for producing
high molecular weight, high atactic polypropylene (very low to almost zero crystalline polymer).
To produce highly isotactic polypropylene the metallocene catalyst should be
a bridged chiral metallocene (preferably containing zirconium) having C2 symmetry with some alkyl substitution in the ring (262). However, with the right substitution others have shown that a C1 -symmetric metallocene can also produce
highly isotactic polypropylene with high T m (161 C) (263).
Early metallocenes were less than desirable polypropylene catalysts because
they produced polymer with low stereocontrol and low molecular weight. Recently
there has been much progress in making high molecular weight, high stereo- and
regioregular polypropylene with relatively high melting points. In general, all
these metallocenes are structurally complicated and the reader should refer to
references cited.
Advantages of Metallocenes. Because they are discreet molecules, one
of the important features of metallocenes is that their structures are easily deduced. This allows almost direct correlation between the catalysts structure
and the microstructure of the polymer produced. This fact allows for a rather
rapid evolution of focused catalyst design to tailor polymer properties to specic needs. For example, one of the early successful metallocenes used in the
isospecic polymerization of propylene was [Et(Ind)2 ]ZrCl2 . By structurally characterizing this compound and making some changes in the bridging group, a new
metallocene was prepared [Me2 Si(Ind)2 ZrCl2 ] which produced a higher molecular

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Table 10. Evolution of the Carbocyclic -ligands and the Effect on Polypropylene
Propertiesa
Metallocene
[Et(Ind)2 ]ZrCl2
[MeSi2 (Ind)2 ]ZrCl2
[MeSi2 (2-Me-4,6-iPr2 (Ind)2 ]ZrCl2
[MeSi2 (2-Me-4-PhInd)2 ]ZrCl2
a Bulk

kg PP/mmol
Zrhr

MW,
g/mol

Melting
point, C

Isotacticity,%
mmmm pentads

188
190
245
755

24,000
36,000
213,000
729,000

132
137
150
157

78.5
81.7
88.6
95.2

polymerization in 1 L of liquid propylene at 70 C, Al/Zr = 15,000 using MAO as activator.

weight polypropylene with high isotacticity and, consequently, a higher melting

point. The evolution of the carbocyclic ligand and subsequent improvement in
isotactic polypropylene properties can be seen in Table 10.
From the standpoint of monomer insertion control, judicious choice of groups
and location on the carbocyclic -ligand produce polypropylene with higher isotacticity, greater molecular weight, and higher melting points.
Polymer Property Advantages. Metallocene catalysts, through variation of catalyst structure, can produce a broad spectrum of polymer microstructures leading to a very wide property envelope which is potentially accessible.
Because of the dened molecular structure of the catalyst, once a catalyst is chosen for a given application, the properties can be precisely controlled.
Some of the property advantages and types of polypropylene and copolymers
of propylene that can be realized with metallocenes are as follows:
(1) Highly tunable tacticity microstructure (isotactic, syndiotactic, atactic,
isoblock/stereoblock, regiospecic microstructures)
(2) Narrow molecular weight distribution
(3) Absence of oligomers and extractables
(4) Improved melting point/extractable balance
(5) Narrow interchain composition distribution in copolymers
(6) Polypropylene with vinyl end groups
(7) Polymerization of expanded comonomer types (including dienes and cycloolens)

Activators/Cocatalysts. As in conventional ZieglerNatta catalysts,

metallocene catalysts must be activated before polymerization of olens can proceed. Methyl aluminoxane (MAO) has been the activator of choice since its discovery by Kaminsky in 1975 (261). MAO is prepared by the controlled hydrolysis of
trimethyl aluminum. The product is a relatively difcult species to characterize.
It consists of oligomers, both linear and cyclic. The composition of the numerous oligomer structures varies depending upon the preparation methods, concentration of the reactants, temperature, and time. The two simplied linear and
cyclic oligomeric alumoxane structures (with a general alleyl group) are shown in
Figure 17.

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Fig. 17. Aluminoxane oligomer structures, linear and cyclic.

Fig. 18. Aluminoxane activating Cp2 ZrCl2 .

The role of MAO in the activation of a metallocene is essentially the same as

in the traditional ZieglerNatta catalyst that is to alkylate the halogenated metal
center. The MAO forms a cationic complex with the metallocene and a dispersed
anionic charge on the aluminoxane. An excess of MAO will lead to dialkylation
of the metallocene metal center. One of the main disadvantages of aluminoxane
activators is the high aluminum concentration level needed; typical AlZr ratios are
over 1000:1. The basic mechanism for the alkylation and activation of a Cp2 ZrCl2
is shown in Figure 18.
Other cocatalysts can be used to activate single-site catalysts. Some
other typical activators, in addition to other alumoxanes, include tetraphenylborate [(C6 H5 )4 B ], tetra(peruorophenyl)borate [(C6 F5 )4 B ], and carborane
(C2 B9 H12 ).
Supportation of Single-Site Catalysts. Without the ability to support
single-site catalysts, the commercial use of these systems would be eliminated in
the numerous bulk and gas-phase polymerization facilities used today. In essence,
they would be restricted to a limited number of slurry processes. The strategy of
supporting a single-site catalyst for an industrial process is much the same as
that for the heterogeneous ZieglerNatta catalysts. The target is a morphologically uniform catalyst particle that is easy to feed into a slurry, bulk-monomer, or
gas-phase process, which produces a polymer that is roughly the same shape as
the catalyst particle but that is 20 to 200 times in volume. In addition the catalyst
particle should be robust and not easily fractured during polymerization. Fracturing of the polymer particle during polymerization produces nes that foul the
process.
There are a number of materials suitable for supporting single-site or metallocene catalysts. These are inorganic oxides, metal halides, and polymers. Among
the inorganic oxides, silica or silica gels have been the supports most widely
used because of their wide range of particle sizes, porosities, etc. More about

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silica supports will be discussed later. Other types of supports, which will not
be discussed in detail, are the other types of inorganic oxides such as aluminas (zeolites type materials), MgO, etc. However, it should be noted that zeolites have shown some promise as supports because of their ordered structures
and precisely known pore sizes. Other support materials are polymers which include polystyrene, derivatized polystyrenes, polysiloxanes, and various polyolens
(porous types of polyethylene and polypropylene) and copolymers. The following
discussions will be predominately focused on silica gel since it is the most widely
used support for metallocenes.
There are essentially three methods in which to make a supportedmetallocene catalyst:
(1) Supporting the metallocene, then treating with an activator
(2) Supporting the activator, then treating with the metallocene
(3) Preparing the metallocene/activator complex in solution, then treating the
support with the complex

Supporting the Metallocene, then Treating with the Activator. Because of their method of preparation, silicas have a high concentration of surface
hydroxyl groups and complexed water. Normally both hydroxyl groups and water will promote decomposition of a metallocene or metallocene/activator complex.
Therefore it is necessary to remove the water either by thermal or chemical dehydration. Full dehydration of silica can occur at 150 C. At this point the silica
gel will have a surface that is fully hydroxylated. Even these hydroxyl groups can
decompose some types of metallocenes. In most cases the silica gel can be further
dehydrated at 400 C (see Fig. 19).
Much work has been reported in the literature on the preparation of silica at various temperatures and under various conditions. Needless to say, the
calcination conditions play a large part in preparing the silica support for the
metallocene.
As far as the actual mechanism of how the metallocene is supported, various
theories abound. However, the metallocene can be connected in two ways to

Fig. 19. The steps to the dehydration of silica gel.

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Fig. 20. Methods of attachment of a metallocene to silica.

the support: (1) through bonding to the metal and the oxygen of the Si O to
create the Si O Metal complex, or (2) by connection of the metallocene to the
support via a linkage through the carbocyclic ligand moiety (Fig. 20). Tethering
the metallocene to the support through the ring system is the method of choice,
but requires preparing specialized carbocyclic ligands, which have spacers with
groups that are able to react with residual OH groups on the silica. In this case it
is necessary to have some remaining hydroxyl groups on the silica.
Supporting the Activator, then treating with the Metallocene. Supporting the alumoxane on the silica support rst and then treating with the metallocene was one of the rst methods used for supporting metallocenes. Many
methods of silica treatment, prior to contacting with the MAO, have been reported. In addition, treatment of the silica gel with solutions of MAO at various
temperatures and pressures, heating with dry MAO, etc, have been reported. All of
these methods have advantages and disadvantages depending on the metallocene,
monomers polymerized, and polymerization conditions used.
Supporting the Metallocene/Activator Complex. The last method to
discuss is the supportation of the Metallocene/MAO complex. In this method the
metallocene and the MAO are reacted in solution to form a complex. The silica is
then treated with the metallocene/MAO solution. The solvent is then evaporated
from the silica support to leave a dry, free-owing catalyst. In some cases the support is held under low pressure while treated with the metallocene/MAO solution
to assist in the impregnation of the catalyst complex into the pores of the silica.
Other methods have been developed which improve the impregnation of the metallocene/MAO complex into the interstitial pores of the support. Concentrating
the catalytic complex into the interior of the support rather than on the surface
improves owability of the supported catalyst system, decreases fouling, and improves the nal polymer morphology. While much is known about the structure of
the single-site catalyst and the properties of the resulting polymers, much of this
changes upon supportation.

Commercialization Aspects of Metallocene/Single-Site Catalysts.

While metallocenes have been known to polymerize olens since the 1950s, only
in the last 10 years have they been introduced commercially. Exxon introduced
its rst generation metallocene in 1989 for the limited production of polyethylene. This was a homogeneous catalyst used in solution. Other companies have
followed with their own metallocene catalyst technologies, which are supported
and are used in solution, gas phase, and supercondensed phases and processes.

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Table 11. Metallocene/SingleSite Technologies

Company
Exxon/Mobil
Basell
Dow
Borealis
JPC/Mitsubishi
TotalFina
Mitsui
Chisso
BP Amoco
a Implies

Technology Name
Univation (Exxpol/Unipol)
Metocene
INSPiRE
Borecene
Proprietary usea
Proprietary usea
Proprietary usea
Proprietary usea
Proprietary usea

Type of Polymer
iPP, impact co-PP (commercial)
iPP, impact co-PP (in development)
iPP (in development)
iPP, impact co-PP (commercial)
iPP, impact co-PP (in development)
iPP (commercial)
sPP (in development)
iPP, sPP (in development)
EPP (in development)

that technology is not commercially available, but the polymer may be commercially

available.

The nonsupported metallocenes are used only in solution processes. The strategies
for market penetration run from targeting commodities to specialty grades.
In the infancy of metallocene catalysis, many companies spent considerable
research dollars on metallocene preparations and understanding the structure of
the metallocene in relation to the polymer properties. In addition to these research
dollars, large expenditures were also made to establish strong patent positions. In
an effort to recoup these expenses for this budding technology, to be competitive,
and to ll voids in their technology portfolios, many have established cooperative
alliances or have consolidated.
At the time of this writing a number of metallocene/single-site catalyst
technologies are available with which to produce polypropylene (see Table 11).
Metallocene-based polypropylenes are commercially available and even catalyst
licenses are available (264).

Manufacturing Processes
The rst commercial processes for the production of polypropylene were batch
polymerization processes using TiCl3 catalysts activated by Al(C2 H5 )2 Cl in a hydrocarbon medium. The hydrocarbon, usually hexane or kerosene, maintained the
isotactic polypropylene in suspension and dissolved the undesirable atactic fraction. After polymerization, the suspension is treated with alcohol to deactivate and
solubilize the catalyst residues, and ltered to separate the residues and atactic
fraction from the desirable polymer, which is then dried. The alcohol and diluent
are recovered by multiple distillations, and the atactic fraction is sold as a byproduct. As the demand for polypropylene increased, these batch polymerization
processes were rapidly replaced by continuous ones, such as the Hercules process
shown in Figure 21. In this process, typical of those used throughout the 1960s
and 1970s, a suspension of TiCl3 catalyst in Al(C2 H5 )2 Cl and kerosene diluent
is continuously fed to the rst of a series of continuous stirred overow reactors.
Monomer is fed to the rst reactors and allowed to react out in the later ones, obviating the requirement for monomer recycle. Typical polymerization temperatures
were in the range of 5570 C and maximum pressures as high as 0.5 MPa (75 psig).

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Fig. 21. Hercules slurry process for polypropylene.

Other similar processes, such as Montedisons, operated at pressures as high as

1.3 MPa (200 psig) with monomer recycle (265). Hydrogen is added to the reactors as required to achieve the desired polymer molecular weight (266). Following
polymerization, the slurry is contacted with isopropyl alcohol, then aqueous caustic to decompose and neutralize catalyst residues. The aqueous phase containing
the alcohol and catalyst residues is separated from hydrocarbon, polymer slurry
phase. The suspended isotactic polymer is separated from the diluent containing
the atactic polymer by continuous ltration or centrifugation, then dried. The alcohol and kerosene are each puried by a series of distillations, then recycled.
Atactic polymer is dried using a thin-lm evaporator and sold as by-product. The
aqueous stream containing catalyst residues is treated prior to disposal of wastewater and inorganic solids. The products available from this technology were limited to homopolymers with relatively high molecular weights (MFR< 15 dg/min),
random copolymers containing low amounts of ethylene, and impact-resistant
copolymers of high molecular weight and low rubber content. Excessive production of soluble polymer causing fouling of heat-transfer surfaces, was the primary
cause of this limitation, more so than the loss of monomer to the production of
less valuable by products. This limitation, and the high energy cost of recycling

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diluent and alcohol, led to the development of processes that eliminated the need
for diluent.
Polymerization in liquid monomer was pioneered by Rexall Drug and Chemical and Phillips Petroleum. In the Rexall process, liquid propylene is polymerized
in a stirred reactor to form a polymer slurry. This suspension is transferred to a
cyclone to separate the polymer from gaseous monomer under atmospheric pressure. The gaseous monomer is then compressed, condensed and recycled to the
polymerizer (267). In the Phillips process, polymerization occurs in loop reactors,
increasing the ratio of available heat-transfer surface to reactor volume (268). In
both of these processes, high catalyst residues necessitate post-reactor treatment
of the polymer.
Gas-phase polymerization of propylene was pioneered by BASF, who developed the Novolen process, using stirred-bed reactors (269). Unreacted monomer is
condensed and recycled to the polymerizer, providing effective removal of the heat
of reaction. As in the early liquid-phase systems, post-reactor treatment of the
polymer is required to remove catalyst residues (270). The high content of atactic
polymer in the nal product limits its usefulness in many markets.
In the 1970s, Solvay introduced an advanced TiCl3 catalyst with high activity and stereoregularity (271). The level of atactic polymer was sufciently low so
that its removal from the product was not required. When this catalyst was used
in liquid monomer processes, residues were sufciently reduced so that simplied
systems for post-reactor treatment were acceptable. Montedison and Mitsui Petrochemical introduced MgCl2 -supported high yield catalysts in 1975 (272). Use of
these catalyst systems reduced the level of corrosive catalyst residues to the extent
that neutralization or removal from the polymer was not required. Stereospecicity, however, was insufcient to eliminate the requirement for removal of the
atactic polymer fraction. These catalysts were used in the Montedison high yield
slurry process, which does not contain the sections required for alcohol treatment,
neutralization, and diluent purication in older slurry processes (265).
Current Processes. Introduction of high yield, high stereoregularity catalysts by Montedison and Mitsui in 1983 enabled the development of processes
in which removal of catalyst and atactic polymer is unnecessary. This enabled
the widespread use of processes in which monomer is the polymerization medium
replacing slurry processes using an inert diluent. Investment and operating costs
were dramatically reduced because of the elimination of the sections of the plant
required for handling and purifying diluent and alcohol, removing catalyst and
separating atactic polymer. Consequently, many companies invested in new plants
either increasing capacity or replacing plants using the older, now obsolete processes. Almost all of the plants built in the past 15 years use one of the simplied processes. Moreover, the production capacity of a newer plant using these
processes is often many times greater than those of earlier plants. Single line
production capacities of 250 kt/y are no longer unusual, and plants with higher
production capacities have been announced. The most widely used processes are
Spheripol, licensed by Basell; Unipol, licensed by Univation; and Novolen, licensed
by Novolen Gmbh.
The Spheripol process consists of one or more loop reactors for production of
homopolymer and random copolymer, and one or more uid bed gas-phase reactors
for the production of the rubber phase for impact-resistant copolymers (Fig. 22).

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Fig. 22. Spheripol process

When producing impact-resistant copolymers, monomer and catalyst components

are fed to the loop reactor for homopolymerization. The use of spherical form catalyst, with a narrow particle size distribution, coupled with high liquid velocities,
minimizes reactor fouling maintaining effective heat transfer and enabling specic outputs in excess of 400 kg PP/hm3 . After polymerization in the loop reactors,
the polymer is separated from the liquid monomer by ashing at a pressure sufcient to allow condensation and recycle of the liquid monomer without recompression. The polymer is then transferred to the gas-phase reactors for the production
of the rubber phase of impact-resistant copolymers. Ethylene and propylene are
fed to the uid bed reactor to produce ethylenepropylene rubber of the desired
composition. Unreacted monomer is recycled and cooled using an external heat
exchanger. The polymer is then separated from the unreacted monomer at a pressure slightly above 1 atm, and then contacted with steam for complete removal of
residual monomer and termination of polymerization (273).
Liquid monomer is polymerized in continuous stirred tank reactors in a number of processes. The Hypol process, developed by Mitsui Petrochemical, uses a
cascaded series of stirred reactors for homopolymerization, followed by uidized
bed gas-phase reactors for copolymerization (274). El Paso (now Huntsman) converted the Rexall liquid monomer process to use high yield catalysts eliminating
the sections required for deashing and removal of atactic material (275). Shell
(now Basell) developed the LIPP process to produce homopolymers and random
copolymers, using their high yield catalysts.
The Unipol PP process developed by Union Carbide (now Dow) and licensed
by Univation, uses a large gas phase uidized bed reactor for the production of
homopolymer and random copolymer. A second, smaller uidized bed reactor is
used in series to produce the rubber required for impact copolymers. The heat of
reaction is removed by cooling the monomer through an external heat exchanger
(Fig. 23). The heat removal capacity of this heat exchanger and, consequently, the

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Fig. 23. The Unipol process.

production capacity of the plant is increased by facilitating condensation of hydrocarbon. This condensing mode technology has enabled this process to be used in
very large single line polymerization plants (patent). Use of high yield catalysts in
the Novolen process (Fig. 24), developed by BASF and licensed by Novolen Gmbh,
has eliminated the problems associated with the use of rst-generation catalysts.
These catalysts enable the plants to achieve high capacity and improve product
quality by minimizing catalyst residues and atactic polymer. This process uses a
single vertical stirred bed reactor for the production of homopolymer and random
copolymer and a second, similar reactor for the production of impact copolymers.
Amoco (now BP) developed a horizontal stirred bed gas-phase reactor that acts
as a series of polymerization stages in a single reactor vessel. This facilitates
the production of homopolymers with broad molecular weight distribution. As in
other processes, a second reactor can be used in series for the production of impact

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Fig. 24. The Novolen process.

copolymers. Basell produces specialty propylene copolymers in the multistage gasphase Catalloy process (276).
The Borstar PP process developed by Borealis can operate at temperatures
above the critical temperature of the reaction medium. This process uses a loop
reactor and gas-phase reactor in series for the production of homopolymer. Additional gas-phase reactors are required for the production of impact copolymers.
The rst commercial scale plant using this process started in 2000. Basell has
announced the development of the Spherizone process using a recirculating gasphase reactor (Covezzi paper). The reactor contains two zones that can be operated
under different conditions, enabling the production of multiphase specialty copolymers in a single reactor. This reactor was rst used in a commercial scale plant
in 2002.

Processing
PP structure can be tailored for use in most polymer processing technologies. The
physical and mechanical properties of PP in the end use product are a function of
both the molecular structure and the processing conditions. The most commonly
used processes for iPP are discussed in the following.
Injection Molding. In the injection molding (qv) process, molten polymer
is injected into a cold mold cavity. During mold lling, the melt is oriented by a
combination of shear and elongational ow (277). Crystallization partially freezes
in this orientation history. Injection-molded iPP articles are made from homopolymers, random and impact copolymers, and lled polymers. Melt ow rates lower

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than 4 dg/min and as high as 100 dg/min in some impact copolymers can be used,
depending on the mold geometry, part thickness, and cycle time desired. Processing conditions vary over a wide range because of the differences in polymer types.
Since iPP melts exhibit shear-thinning properties, high injection pressures and
high shear rates are used to promote the lling of the mold. Higher melt ow
(lower molecular weight) polymers provide more uniform ow and low cycle times
in parts with thin sections. Lower melt ow (higher molecular weight) polymers
are employed when toughness is required, and can be used in parts that have
thicker cross sections. Melt temperature varies with the melt-ow rate of the
polymer and the mold shape. Higher temperatures reduce the melt viscosity and
facilitate mold lling; however, the cycle time is increased. Melt temperatures as
low as 200 C can be used with high melt-ow polymers; higher melt temperatures
are required with low melt-ow polymers. Mold temperatures typically range from
20 to 50 C. Lower mold temperatures reduce the cycle time, but may produce a
rough or low gloss surface. Orientation is an important determinant of properties and related to the skin layer thickness (see MORPHOLOGY). Melt temperature,
melt-ow rate (MFR), polydispersity, and proximity to the mold gate inuence
skin thickness (120,278286). Lower values result from higher melt temperature
and MFR, and lower polydispersity. Regions far from the gate also have lower
values. Molds should be designed to minimize localized stresses and ensure mold
lling. When nonuniform wall thickness is required, it should decrease gradually
in the ow direction. Like all crystalline thermoplastics, iPP is sensitive to failure at notches, and smooth radii are recommended at all sharp angles, corners, or
ribs. Mold shrinkage varies with thickness from 1 to 2.5%. Thicker sections shrink
more than thinner sections.

Fiber.
Melt Spinning. Melt spinning produces a broad range of iPP bers, ranging
from short staple ber to continuous lament (CF) or bulked/textured continuous
laments (BCF) (see OLEFIN FIBERS). The tex per lament of the as-spun laments,
where tex is the mass of ber (g) per 1000 m of length, is typically in the range
of 0.147.78 tex (1.370 dpf). The lower end of this range corresponds to ne
laments of 15-m diameter. Noncircular cross sections can be used to modify
ber appearance.
Melt spinning of iPP typically involves forcing molten polymer through a
spinnerette (a collection of small-diameter orices) and collecting it, typically on a
take-up reel, some distance from the spinnerette at a velocity exceeding the orice
velocity. The tension provided by the take-up reel (melt drawing) provides partial
orientation which greatly inuences the nal properties of the ber. Yarns are
collections of individual laments, and can range from monolaments to several
thousand laments depending on the process. Spinning speeds can approach 3000
m/min or higher in some cases. The iPP melt expands upon exiting the holes, a
phenomenon known as extrudate die swell (287). The diameter of the extruded lament just after the die plate can typically increase on the order of 30100% relative
to the spinnerette hole depending on resin structure (melt ow rate, polydispersity). The swelling increases as the size of the die holes is reduced. This factor, and
most often more importantly the maximum sustainable spin speed, determines the
minimum diameter of melt-spun iPP bers. During the spinning process, a uid
element experiences an acceleration (increase of velocity), decreasing temperature

342

PROPYLENE POLYMERS

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due to a high rate of cooling, and decreasing diameter with increasing distance
along the spin line (288). Large vertical air-cooling chambers, or chimneys, as high
as 15 m can be required to cool the molten lament and allow adequate time for
crystallization under the applied extensional force. Short spin processes generally
use low spinning speeds to minimize the space required for quenching.
Fiber properties depend on the complex interrelationship of polymer structure (polydispersity, molecular weight, tacticity), processing conditions (melt temperature, melt throughput, spinnerette design, spin speed, cooling rate), and
equipment design. Both material and processing variables inuence the die swell,
extensional melt rheology, maximum spin speed, crystallization/nucleation characteristics along the spin-line, and ber orientation. Controlled rheology resins
with narrow polydispersity are often used to improve the balance of spinning
performance and ber properties. Metallocene iPP resins have been introduced
as an alternative technology (289,290). The tenacity (ultimate stress) of individual as-spun laments is generally in the range of 0.0880.353 N/tex (14 g/den).
Break elongation decreases and tenacity increases with increasing spin speed due
to increasing orientation. Post-drawing of laments in the solid state below the
polymer melting point, either via in-line continuous or off-line batch processes,
further increases the tenacity of the bers by improving ber orientation. Drawing is generally carried out at temperatures exceeding 70 C, with draw ratios in
the 210 range. The drawability is a function of the starting morphology, polymer
structure, draw rate, and draw temperature. The ultimate tenacity of perfectly
oriented iPP bers has been estimated to be 1.32 N/tex (15 g/den) (121), though
most commercial drawn bers have tenacities of 0.3530.794 N/tex (49 g/den). A
heat setting, or annealing process below the polymer melting point, can minimize
ber shrinkage.
Melt Blowing. The melt-blowing process uses very high melt-ow rate (low
molecular weight) iPP, sometimes in excess of 4001500 dg/min. These melt-ow
rates are much higher than for melt-spinning operations. The ow of molten,
low viscosity polymer, extruded through a small die is disrupted by high velocity
hot air. A large volume of cooling air fed near the die exit quenches the bers
and deposits them on a collecting screen as a mat of entangled bers. Processing
conditions and polymer structure can be varied to alter the lament diameter,
characteristics of the collected mat, and undesirable large shots, or polymer
particles. Very ne bers, less than 5 m in diameter, can be produced. The ber
entanglement is sufcient to maintain the integrity of the web, and thermal bonding is not necessary. Fabrics produced by this process are very soft because of the
small ber diameter. Because the bers are not highly oriented or bonded, meltblown fabrics usually have low tensile strength. Meltblown fabrics have improved
barrier properties to aqueous liquids relative to spun-bonded fabrics.
Spun Bonded Fabrics. Spun bonded fabrics are produced by depositing
extruded, spun laments onto a collecting belt in a uniform randomized manner,
followed by thermal bonding of the laments. Polymers with melt-ow rates above
20 dg/min and narrow polydispersity improve stability during ber formation
and adequate melt throughput. The bers are separated during the web-laying
process by air jets and the collecting belt is usually perforated to prevent the air
stream from deecting and carrying the bers in an uncontrolled manner. Thermal
bonding, using heated embossing rolls or hot needles, imparts strength to the web

Vol. 11

PROPYLENE POLYMERS

343

by fusing some of the bers. This process can be combined with the melt-blowing
process to produce soft, multilayer fabrics with good tensile properties. In these
multilayer structures the meltblown fabric provides barrier resistance and the
spun bonded fabric imparts strength.
Slit and Split Films. Thick industrial-grade yarns are often produced by
slitting lms, providing a less expensive alternative to direct extrusion. Cast lm is
slit in the machine direction by parallel rotary knives. The resulting tape can then
be cold drawn in an oven below the polymer melting point, in a manner similar to
drawn melt spun bers, to produce the nal ber. Draw ratios of 411 are common.
Higher draw ratios produce higher tenacity. The width of the slit tapes depends
on the spacing between knives and the draw ratio. Knife spacings as low as 1
mm are sometimes used to produce textile bers, although spacings of 1035 mm
are more common. Tapes produced by slitting a fully drawn lm are wider than
those oriented after slitting because of the physical limitations on minimum knife
spacing. An alternative approach is to directly extrude the tapes prior to drawing.
The tapes are annealed to minimize shrinkage. Fibers from split or brillated lms
are formed by the drawing of polypropylene lm to the degree that it splits into
numerous ber-like interconnected tapes. In some processes the draw-induced
splitting is mechanically augmented by gears, rollers, or gas jets (291).

Film.
Cast Film. The rst commercial iPP lms were produced by extrusion casting. Polymer is extruded through a slit or a tubular die and quenched by cooling
on chill rolls or in a water bath. Cast lm is not highly oriented and consequently
does not have the stiffness of oriented lms. Resins are typical iPP homopolymer
or random copolymers. Random copolymers have improved clarity, and somewhat
improved impact resistance. Rapid quenching often results in conversion to the
mesomorphic form, which can be advantageous for lm clarity. This tendency is
greater in random copolymers than in homopolymer. High chill roll temperatures
can result in hazy lms, while chill roll temperatures which are too low (below
the dew point of the ambient air) can result in water condensation on the lm.
Additives such as antiblock and slip agents are often added for improved handling
of the lm rolls.
Biaxially Oriented Polypropylene. Orientation improves the strength of
iPP lms. Biaxially oriented polypropylene (BOPP) lms have higher strength
and stiffness than cast lms and consequently can often be used in much thinner
gauges. Homopolymers are used almost exclusively to provide maximum stiffness
and water-vapor barrier. Oriented lms are produced by the tenter frame and
tubular blown or double bubble methods. Most of the newly installed capacity has
utilized the tenter frame process, taking advantage of the economics of the large,
high capacity units available. The trend is to ever increasing line speeds, with
300 m/min not uncommon. In the tenter frame process, iPP is melt extruded
through a slot die to form a sheet after quenching onto a cast roll. The cast sheet is
heated to a temperature below the melting point, and drawn. In the case of sequential orientation, the softened cast sheet is drawn by a series of rolls to the desired
draw ratio in the machine (longitudinal) direction, and subsequently clamped by
a series of clips and conveyed into a tenter oven where it is subsequently drawn
in the transverse direction to the desired draw ratio by the divergent chain clips.
In the bubble process, a tube is extruded, quenched, and radially expanded by

344

PROPYLENE POLYMERS

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ination with air to provide transverse orientation. Axial orientation is provided

by extension in the machine direction through a series of nip rolls. The tube is
then attened and slit into at lm. Orientation in both processes is provided by
stretching below the melting point. The drawing process is strongly correlated to
the crystallinity at the draw temperature which is closely related to the stereoregularity of the resin. Generally there is a trade-off between processability and
nal lm mechanical and barrier properties. Heat aging under slight tension at
a temperature above the orientation temperature but below the melting point
minimizes subsequent shrinkage. Opaque lms are produced by introducing microvoids into the lm during the orientation by introducing small particles during
extrustion. During orientation, microvoids are created as the polymer expands
from the inelastic solid. Untreated oriented iPP lms are not easily heat sealed.
Consequently, lower melting random copolymers and terpolymers are often coextruded with the homopolymer to form a heat sealing layer.
Blow Molding. Low melt ow polymers are used in blow molding (qv)
to provide the melt strength required to maintain stability of the parison, ie,
a molten, thick-walled tube of melt. High density polyethylene has been more
commonly used to form large parts because of its greater stability; however, a
number of improved polypropylene grades are suitable for these applications (292).
In extrusion blow molding, the extruded parison hangs freely before entering
the mold, and low melt temperatures (between 205 and 215 C) are preferred. In
injection blow molding, a preform is injection-molded on a steel rod, transferred to
a blow molding mold, and blown. Consequently, the melt strength requirements
of extrusion molding is alleviated to some extent, and higher melt temperatures
can be used. Injection stretch blow molding produces a biaxially oriented part
with higher stiffness, lower temperature impact strength, and greater clarity.
The parison is cooled after it is formed by extrusion or injection molding, reheated
to the desired orientation temperature, mechanically stretched, and then formed
into the desired shape by blowing. Random copolymers of intermediate melt-ow
rate (10 MFR) have improved processing characteristics.
Extrusion and Thermoforming. iPP is extruded into sheet, usually for
subsequent stamping or thermoforming (qv), or into pipes and proles (see EXTRUSION). Low melt ow rate resins are used to provide the melt strength required to
maintain uniformity. The choice of resin can often be dictated by subsequent forming operations. High melt strength polymers, produced by post-polymerization
modication of conventional iPP, improve uniformity. Care must be taken for proles of complicated geometry due to dimensional changes on crystallization, and
variable cooling rate for regions differing in thickness. Good mixing of the melt
during the extrusion process is important. Melt temperatures which are too high
can promote degradation, leading to loss of properties, discoloration, and plate out
which is the migration of additives and/or low molecular weight polymer to the
surface of the sheet or prole. Lower temperatures reduce throughput and uniformity and lead to higher levels of orientation detrimental to subsequent forming.
In the thermoforming process, the sheet is extruded either in-line or off-line
and formed, either in melt phase or solid phase, into a part of desired shape. Sheet
uniformity is important. Historically, iPP has not been used in conventional meltphase thermoforming equipment because of its narrow forming temperature range
and the tendency of the melt to sag. Controlling the sag is particularly important

Vol. 11

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345

for large parts or multiple cavities. The introduction of newer iPP grades with
higher melt strength and improved sag resistance has increased the use of iPP
in conventional melt-phase thermoforming equipment (293). Processes such as
Shells solid-phase pressure forming (294) were developed to overcome problems
associated with melt forming. The iPP article is formed at temperatures close
to but below the crystalline melting point, by stretching the sheet into the mold
cavity with a shaped plug. The part is forced against the mold surface by cold
air to obtain the desired shape. Manufacturers of thermoforming equipment have
also modied their processes to effectively utilize iPP (295).
Stabilization. Polypropylene is subject to attack by oxygen, radiation, and
excessive heat causing a loss of molecular weight and physical properties. Stabilizers are added to the polymer to minimize these effects. Small quantities of
hindered phenolic antioxidants (qv) are added in the polymerization plant, usually in the drying section, to protect the polymer against degradation (qv) during
short-term storage. Typically 2,6-di-tert-butyl-p-cresol (BHT) and octadecyl 3,5di(tert-butyl-4-hydroxy)hydrocinnamate (Irganox 1076) are used. The bulk of the
stabilizer is added during pelletization or fabrication to protect the polymer during
processing or in the nal application. Typical stabilization formulations include a
hindered phenolic antioxidant, possibly with a thiodipropionate synergist, a phosphite to provide high temperature melt stabilization, and an acid scavenger such
as calcium stearate or dihydrotalcite (296). Hindered phenols limit the propagation of alkyl radicals and the resulting chain scission. Thiodipropionic acid esters
act to decompose peroxides formed by polypropylene oxidation. More importantly,
the sulfonic acid intermediate of thiodipropionate oxidation acts as a scavenger for
the free radicals formed by the decompositon of phenols, increasing the effectiveness of the phenolic antioxidant (297). Phosphites also act to decompose peroxides
and are most effective at the temperatures usually encountered in processing. The
acid scavenger acts to prevent the reactions between hindered phenols and metal
chlorides that can form colored titanium phenolates, as well as minimize equipment corrosion. Protection against ultraviolet radiation is usually provided by a
hindered amine light stabilizer (HALS), such as Tinuvin 770 (see UV STABILIZERS).
Stabilization (qv) of polypropylene has been reviewed (157).

Economic Aspects
Polypropylene consumption continues to increase more rapidly than the economy
and most other thermoplastics. Although the comparative growth in polypropylene consumption has slowed from that in the 1970s and 1980s, the relative share
of polypropylene use in North America has increased from 17% to 20% of all
thermoplastics during the 1990s (298). The annual increase in consumption of
polypropylene in North America averaged about 7% through the same period (299).
Consumption in Western Europe has also increased at a similar rate. Growth
in Japan has been much slower than in other countries, in part because of the
protracted Japanese recession in the late 1990s, but also because of competition
from the emerging economies in East Asia. The rapid growth of the Asia/Pacic
region has been the major economic story of the past decade, and the growth in
polypropylene consumption and production has been phenomenal. This region is

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PROPYLENE POLYMERS

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Table 12. World Consumption of Polypropylene, 103 tona,b

Country

1994

1995

1996

1997

1998

1999

2000

2001

United States
Canada
Mexico
Brazil
Western Europe
Japan
China
India

4145
293
236
374
5030
2080

4220
358
219
527
4979
2219

4654
379
227
537
5440
2365

5063
368
285
584
5766
2439

5412
361
310
612
6278
2268
3100
763

6350

6439

7317

687
6795
2298
3535
931

6976
2756
4230
1026

7360
2734

a Ref.
b U.S.

1194

300.
consumption in 2002 was 7748 103 t (301).

now the worlds largest market for polypropylene, accounting for almost 40% of
supply and demand (302). China has developed as one the worlds major markets
for polypropylene and other thermoplastics, and is the leading importer of plastics, despite a signicant increase in its production capacity. World consumption
data for polypropylene are listed in Table 12. Malaysia, South Korea, India, and
Thailand have joined Taiwan as signicant producers, with the construction of
modern, world-scale manufacturing plants. Brazil, the largest market in Latin
America, has also grown at a rapid pace.
This increase in consumption has, however, been more than matched by a
larger increase in production capacity, fostering a situation of oversupply and low
capacity utilization. New plants often have production capacities of 250 kt/y to capitalize on the economy of large-scale facilities. In North America, where renery
propylene is the source for most monomer, the decision to invest in polypropylene
capacity is often related to the need to market propylene. Arco Products (now part
of BP) and Tosco (now owned by Phillips) both decided to produce polypropylene
as the most cost-effective way to eliminate regulatory problems caused by excess
propylene production at their reneries. Arco/Tosco capacity increased by 23%
from 1998 to 2001; however, consumption only increased by 17% over the same
period. Capacity utilization dropped to the lowest levels since 1989. Producers
prot margins have decreased dramatically as the polymer prices have fallen relative to the cost of production. These prot margins are highly dependent upon
the difference between the price of polymer and the price of propylene monomer.
Monomer prices are related to oil prices; however, polymer prices are related to
supply and demand. This difference has decreased consistently through the past
decade, as some producers have been willing to supply at the lower prices. It has
been estimated that a signicant number of producers have been operating at a
loss (303). Consequently, producers reduced capacity by closing or idling plants.
Table 13 gives world production data, and Table 14 gives world capacity information and Table 15 gives U.S. production and capacity for the years 20002002.
The 4% decrease in polypropylene capacity in 2002 is unprecedented in North
America. Excess capacity and low prot margins characterize the polypropylene
industry throughout the world, not just in North America, as the industry has
become globalized. The market situation in Asia can dramatically affect prices in
North America and Europe as imports into that region increase or decrease.

Vol. 11

PROPYLENE POLYMERS

347

Table 13. World Production of Polypropylene, 103 tona

Country

1994

1995

1996

1997

1998

1999

United States
4326
Canada
258
Mexico
170
Brazil
535
Western Europe
Japanb
2248

4939
329
227
557

5438
320
210
590

6041
320
196
636

6270
322

7026

707

767

2488

2683

2788

2597

2678

a Ref.

300.
production in Japan, 2760 103 t (302).

b 2001

Table 14. World Capacity of Polypropylene, 103 tona

Country

1994

1995

1996

1997

1998

1999b

United States
Canada
Mexico
Brazil
Western Europe
Japan
China
South Korea
India
Taiwan
Thailand

4644
324
249

5433

5911

6453

7001

796

778

755

785

2454
841
1696
349
469
359

888
2025
490
479
580

1257
2175
745
489
800

1423
2620
791
798
1088

7732
324
220
912
8166
3063
1503

a Ref.
b For

1705
161
460
310

300.
countries other than U.S., Ref. 304.

Table 15. United States Production and Capacity of

Polypropylene, 103 ton, for 20002002a

Production
Capacity
a Ref.

2000

2001

2002

7138
8117

7226
8620

7690
8241

301.

To combat the decrease in protability major producers have chosen to reduce costs through mergers. Royal Dutch/Shell and BASF have merged their polyolen activities, formerly Montell, Elenac and Targor, to form Basell, which is the
worlds largest producer of polypropylene. This company contains facilities that
were once part of BASF, Hercules, Hoechst, ICI, Montedison, and Shell. Borealis,
one of the largest European producers and the result of a merger between the
polyolen businesses of Statoil and Neste, acquired PCD and OMV, two smaller
producers. Major mergers of large petroleum companies, such as Exxon and Mobil (ExxonMobil), BP, Amoco and ARCO (BP), and Total, Elf Aquitane and Fina
(TotalFina) have also resulted in the combination of their polymer operations.
The Dow Chemical Co. purchased Union Carbide, combining the polypropylene
businesses of the two companies. Japanese producers afliated with Mitsui have

Table 16. Distribution of Polypropylene by Principal North American Market, 103 ton

348

Market

1994

1995

1996

1997

1998

1999

2000

2001

(Growth)

2002

(Growth)

Transportation
Packaging
Building and construction
Electrical/electronic
Furniture and furnishings
Consumer and institutional
All other
Exports
Total

281
922
115
147
766
1091
892
297
4511

342
1036
0
162
866
1215
904
332
4857

329
1104
0
180
937
1283
1200
463
5497

352
1182
0
193
1003
1373
1285
565
5952

378
1270
0
207
1078
1476
1381
489
6278

334
1614
171
185
834
1538
1784
539
7000

337
1586
179
155
913
1497
1771
629
7067

323
1578
159
156
829
1510
1784
856
7317

(0.051)
0.089
0.066
0.038
0.034
0.075
0.104
0.016
0.068

345
1851
168
164
923
1661
1878
758
7748

(0.053)
0.096
0.065
0.039
0.041
0.077
0.099
0.004
0.068

Vol. 11

PROPYLENE POLYMERS

349

Table 17. Consumption of Polypropylene by Use in North America, 103 ton

USe

1994

1995

1996

1997

1998

1999

2000

2001

Injection molding
Appliances
Consumer products
Rigid packaging
Transportation
Other
Blow molding
Extrusion
Film
Sheet
Fiber
All other
Other End Use
Total

1498
120
598
390
229
162
75
1834
420
72
1275
67
806
4214

1665
129
539
438
281
278
80
2048
488
108
1391
60
732
4525

1765
142
611
484
262
266
78
2184
514
104
1505
63
1006
5034

1655
116
695
545
185
109
78
2209
525
108
1499
77
1446
5387

1818
134
768
609
215
93
81
2382
548
116
1645
73
1508
5789

2108
150
923
674
251
110
84
2546
598
141
1729
77
1724
6461

2068
113
898
712
259
86
66
2587
609
150
1732
96
1718
6439

2158
118
938
795
244
63
81
2478
601
196
1593
88
1744
6461

merged operations to form Grand Polymers and those afliated with Mitsubishi
have formed Japan Polychem. Mitsui and Sumituomo have announced a merger
of their chemicals businesses, and included polypropylene. At the end of 2001,
the largest producers of polypropylene in order of capacity are Basell, BP, Atona,
ExxonMobil, and Dow Chemical (305). In Europe, the largest producers are Basell,
Borealis, Atona, Sabic, and BP, respectively.
The principal market applications of polypropylene in North America are
shown in Table 16. The use of polypropylene in packaging has grown more rapidly
than other areas because of its increased use in injection-molded containers and
packaging lms. The consumer and institutional products sector is the largest
market for polypropylene. This sector is the most diverse and includes nonwoven polypropylene fabrics in baby diapers as well as injection-molded toys and
houseware. This market has also grown considerably in the past decade. The consumption of polypropylene in furniture and furnishings, which includes carpet
ber, continues to be one of the major applications, but is growing more slowly
than overall consumption. The use of polypropylene in transportation, primarily
automobiles, is not growing as fast as other areas. Consumption of polypropylene
in injection-molded transportation applications has declined in recent years, as
shown in Table 17. Polypropylene is most commonly extruded into bers or lms,
or injection molded. Other fabrication processes are not used as frequently.

BIBLIOGRAPHY
Propylene Polymers in EPST 1st ed., Vol. 11, pp. 597619, by J. L. Jezl, Avisun Corp.,
and E. M. Honeycutt, Patchogue Plymouth Co.; in EPSE 2nd ed., Vol. 13, pp. 464531,
by Richard B. Lieberman, Himont Research and Development Center, and Pier Camillo
Barbe, Himont Italia, Centro Recerche Guilio Natta, Italy.
1. G. L. Yaws, Physical Properties, McGraw-Hill Inc., New York, (1977).
2. R. W. Gallant, Physical Properties of Hydrocarbons, Vol. 1, Gulf Publishing Co., Houston, Tex., (1968).

350

PROPYLENE POLYMERS

Vol. 11

3. R. C. Reid, J. M. Prausnitz, and T. K. Sherwood, The Properties of Gases and Liquids,

3rd ed., McGraw-Hill Inc., New York, (1977).
4. H. H. Brintzinger, D. Fischer, R. Mulhaupt, B. Rieger, and R. M. Waymouth, Angew.
Chem., Int. Ed. Engl. 34, 1143 (1995).
5. G. H. Llinas, S.-H. Dong, D. T. Mallin, M. D. Rausch, Y.-G. Lin, H. H. Winter, and
J. C. W. Chien, Macromolecules 25, 1242 (1992).
6. E. Hauptman, R. M. Waymouth, and J. W. Ziller, J. Am. Chem. Soc. 117, 11586 (1995).
7. W. J. Gauthier, J. F. Corrigan, N. J. Taylor, and S. Collins, Macromolecules 28, 3771
(1995).
8. E. A. Youngman and J. Boor, Macromol. Rev. 2, 33 (1967).
9. A. Zambelli and C. Tosi, Adv. Polym. Sci. 32, 15 (1974).
10. C. Wolfsgruber, G. Zannoni, E. Rigamonti, and A. Zambelli, Makromol. Chem. 176,
2765 (1975).
11. A. Zambelli, P. Locatelli, G. Zannoni, and F. A. Bovey, Macromolecules 11, 923 (1978).
12. F. C. Shilling and A. E. Tonelli, Macromolecules 13, 270 (1980).
13. Y. Doi, T. Suzuki, and T. Keii, Makromol. Chem. Rapid Commun. 2, 293 (1981).
o, Polym. J. 15, 859 (1983).
14. S. N. Zhu, X. Z. Yang, and R. Chuj
15. J. A. Ewen, J. Am. Chem. Soc. 106, 6355 (1984).
anen,

16. R. Paukkeri, T. Va an
and A. Lehtinen, Polymer 34, 2488 (1993).
17. M. Farina, G. DiSilvestro, and P. Sozzani, Macromolecules 26, 946 (1993).
18. V. K. Gupta, S. Satish, and I. S. Bhardwaj, J. Macromol. Sci., Rev. Macromol. Chem.
Phys. 34, 439 (1994).
19. R. Paukkeri, E. Iiskola, A. Lehtinen, and H. Salminen, Polymer 35, 2636 (1994).
20. V. Busico, P. Corradini, R. DeBiasio, L. Landriani, and A. L. Segre, Macromolecules
27, 4521 (1994).
21. M. Farina, G. DiSilvestro, and A. Terragni, Macromol. Chem. Phys. 196, 353 (1995).
22. M. D. Bruce and R. M. Waymouth, Macromolecules 31, 2707 (1998).
23. R. A. Phillips and M. D. Wolkowicz, in E. P. Moore Jr., ed., Polypropylene Handbook,
Hanser, Munich, 1996.
24. V. Busico, R. Cipullo, and P. Corradini, Makromol. Chem. 194, 1079 (1993).
25. V. Busico, R. Cipullo, and P. Corradini, Makromol. Chem., Rapid Commun. 14, 97
(1993).
26. V. Busico, R. Cipullo, J. C. Chadwick, J. F. Modder, and O. Sudmeijer, Macromolecules
27, 7538 (1994).
27. T. Tsutsui, N. Kashiwa, and A. Mizuno, Makromol. Chem., Rapid Commun. 11, 565
(1990).
28. J. C. Chadwick, A. Miedema, and O. Sudmeijer, Macromol. Chem. Phys. 195, 167
(1994).
29. J. C. Chadwick, G. M. M. van Kessel, and O. Sudmeijer, Macromol. Chem. Phys. 196,
1431 (1995).
30. E. Albizzati, U. Giannini, G. Collina, L. Noristi, and L. Resconi, in E. P. Moore Jr., ed.,
Polypropylene Handbook, Hanser, Munich, 1996.
31. K. Soga, T. Shiono, S. Takemura, and W. Kaminsky, Makromol. Chem. Rapid Commun.
8, 305 (1987).
32. A. Grassi, A. Zambelli, J. L. Resconi, E. Albizzati, and R. Mazzocchi, Macromolecules
21, 617 (1988).
33. A. Toyota, T. Tsutsui, and N. Kashiwa, J. Mol. Catal. 56, 237 (1989).
34. T. Tsutsui, N. Ishimaru, A. Mizumo, A. Toyota, and N. Kashiwa, Polymer 30, 1350
(1989).
35. H. N. Cheng and J. A. Ewen, Makromol. Chem. 190, 1931 (1989).
36. W. Roll, H.-H. Brintzinger, B. Rieger, and R. Zolk, Angew. Chem., Int. Ed. Engl. 29,
279 (1990).

Vol. 11

PROPYLENE POLYMERS

351

37. B. Rieger, X. Mu, D. T. Mallin, M. D. Rausch, and J. C. W. Chien, Macromolecules 23,

3559 (1990).
38. J. C. W. Chien and R. Sugimoto, J. Polym. Sci., Polym. Chem. Ed. 29, 459 (1991).
39. D. Fischer and R. Mulhaupt, Macromol. Chem. Phys. 195, 1433 (1994).
40. U. Stehling, J. Diebold, R. Kirsten, W. Roll, H. H. Brintzinger, S. Jungling, R. Mulhaupt
and F. Langhauser, Organometallics 13, 964 (1994).
41. L. Resconi, A. Fait, F. Piemontesi, M. Colonnesi, H. Rychlicki, and R. Zeigler, Macromolecules 28, 6667 (1995).
42. F. A. Bovey, High Resolution NMR of Macromolecules, Academic Press, Inc., New
York, 1972.
o, Y. Kogure, and T. Va an
anen,

43. R. Chuj
Polymer 35, 339 (1994).
onen, J. V. Seppal
a,
R. Chuj
o, and Y. Kogure, Polymer 36, 1499 (1995).
44. M. Hark
45. Y. Doi, Makromol. Chem., Rapid Commun. 3, 635 (1982).
46. D. R. Bureld and P. S. T. Loi, J. Appl. Polym. Sci. 36, 279 (1988).
47. R. Paukkeri and A. Lehtinen, Polymer 34, 4075 (1993).
48. G. Natta, G. Mazzanti, G. Crespi, and G. Moraglio, Chim. Ind. 39, 275 (1957).
49. J. B. P. Soares and A. E. Hamielec, Polymer 36, 1639 (1995).
50. U. S. Pat. 5,302,897 (Apr. 12, 1994), R. L. Dechene, T. B. Smith, S. A. Marino, J. Tache,
and A. Roy (to Auburn International).
51. M. G. Styring and A. E. Hamielec in A. R. Cooper, ed., Determination of Molecular
Weight, John Wiley & Sons, Inc., New York, 1989.
52. P. J. Flory, Principles of Polymer Chemistry, Cornell University Press, Ithaca, N.Y.,
1953.
53. H. Coll, in A. R. Cooper, ed., Determination of Molecular Weight, John Wiley & Sons,
Inc., New York, 1989.
54. A. R. Cooper, in A. R. Cooper, ed., Determination of Molecular Weight, John Wiley &
Sons, Inc., New York, 1989.
55. B. Chu, in A. R. Cooper, ed., Determination of Molecular Weight, John Wiley & Sons,
Inc., New York, 1989.
56. M. Kurata and Y. Tsunashima, in J. Brandrup, E. H. Immergut, and E. A.
Grulke, eds., Polymer Handbook, 4th ed., John Wiley & Sons, Inc., New York,
1999.
57. Th. G. Scholte, N. L. J. Meijerink, H. M. Schoffeleers, and A. M. G. Brands, J. Appl.
Polym. Sci. 29, 3763 (1984).
58. I. Pasquon, Pure Appl. Chem. 15, 465 (1967).
59. J. B. Kinsinger and R. E. Hughes, J. Phys. Chem. 63, 2002 (1959).
60. P. Parrini, F. Sebastiano, and G. Messina, Makromol. Chem. 38, 27 (1960).
61. G. Zeichner and P. Patel, 2nd World Congress of Chemical Engineering, Montreal,
P. Q., Canada, 1981.
62. W. W. Graessley, The Entanglement Concept in Polymer Rheology, Advance Polymer
Science Series 16, Springer-Verlag, New York, 1974.
63. G. Natta and P. Corradini, del Nuovo Cimento XV, 40 (1960).
64. B. Lotz, J. C. Wittmann, and A. J. Lovinger, Polymer 37, 4979 (1996).
65. S. Bruckner, S. V. Meille, V. Petraccone, and B. Pirozzi, Prog. Polym. Sci. 16, 361
(1991).
66. A. J. Lovinger, B. Lotz, D. D. Davis, and F. J. Padden Jr., Macromolecules 26, 3494
(1993).
67. C. DeRosa and P. Corradini, Macromolecules 26, 5711 (1993).
68. A. J. Lovinger, B. Lotz, D. D. Davis, and M. Schumacher, Macromolecules 27, 6603
(1994).
69. W. Stocker, M. Schumacher, S. Graff, J. Lang, J. C. Wittmann, A. J. Lovinger, and
B. Lotz, Macromolecules 27, 6948 (1994).

352

PROPYLENE POLYMERS

Vol. 11

70. P. Corradini, V. Petraccone, C. DeRosa, and G. Guerra, Macromolecules 19, 2699

(1986).
71. P. Corradini, C. DeRosa, G. Guerra, and V. Petraccone, Polym. Commun. 30, 281 (1989).
72. S. V. Meille, D. R. Ferro, S. Bruckner, A. J. Lovinger, and F. J. Padden, Macromolecules
27, 2615 (1994).
73. D. L. Dorset, M. P. McCourt, S. Kopp, M. Schumacher, T. Okihara, and B. Lotz, Polymer
39, 6331 (1998).
74. B. Rieger, X. Mu, D. T. Mallin, M. D. Rausch, and J. C. W. Chien, Macromolecules 23,
3559 (1990).
75. D. Fischer and R. Mulhaupt, Macromol. Chem. Phys. 195, 1433 (1994).
76. R. Thomann, C. Wang, J. Kressler, and R. Mulhaupt, Macromolecules 29, 8425
(1996).
77. K. Mezghani and P. J. Phillips, Polymer 39, 3735 (1998).
78. S. Bruckner and S. V. Meille, Nature 340, 455 (1989).
79. S. V. Meille, S. Bruckner, and W. Porzio, Macromolecules 23, 4114 (1990).
80. B. Lotz, S. Graff, C. Staupe, and J. C. Wittmann, Polymer 32, 2902 (1991).
81. D. R. Ferro, S. Bruckner, S. V. Meille, and M. Ragazzi, Macromolecules 25, 5231 (1992).
82. A. J. Lovinger and B. Lotz, J. Polym. Sci., Part B: Polym. Phys. 35, 2523 (1997).
83. I. Rodriguez-Arnold, Z. Bu, and S. Z. D. Cheng, J. Macromol. Sci., Rev. Macromol.
Chem. Phys. C 35, 117 (1995).
84. P. Sozzani, R. Simonutti, and M. Galimberti, Macromolecules 26, 5782 (1993).
85. A. Marigo, C. Marega, and R. Zannetti, Macromol. Rapid Commun. 15, 225 (1994).
86. C. DeRosa, F. Auriemma, and V. Vinti, Macromolecules 30, 4137 (1997).
87. C. DeRosa, F. Auriemma, and V. Vinti, Macromolecules 31, 7430 (1998).
88. C. DeRosa, F. Auriemma, V. Vinti, and M. Galimberti, Macromolecules 31, 6206 (1998).
89. F. Auriemma, R. H. Lewis, H. W. Spiess, and C. DeRosa, Macromol. Chem. Phys. 196,
4011 (1995).
90. F. Auriemma, R. Born, H. W. Spiess, C. DeRosa, and P. Corradini, Macromolecules 28,
6902 (1995).
91. F. Auriemma, C. DeRosa, O. Ruiz de Ballesteros, and P. Corradini, Macromolecules
30, 6586 (1997).
92. C. DeRosa, F. Auriemma, V. Vinti, A. Grassi, and M. Galimberti, Polymer 39, 6219
(1998).
93. J. Loos, A. M. Schauwienold, S. Yan, J. Petermann, and W. Kaminsky, Polym. Bull.
38, 185 (1997).
94. T. Nakaoki, Y. Ohira, H. Hayashi, and F. Horii, Macromolecules 31, 2705 (1998).
95. Y. Ohira, F. Horii, and T. Nakaoki, Macromolecules 33, 5566 (2000).
96. G. Natta, M. Peraldo, and A. Allegra, Makromol. Chem. 75, 215 (1964).
97. Y. Chatani, H. Maruymama, T. Asanuma, and T. Shiomura, J. Polym. Sci., Polym.
Phys. 29, 1649 (1991).
98. D. R. Bureld, P. S. T. Loi, Y. Doi, and J. Majzik, J. Appl. Polym. Sci. 41, 1095 (1990).
99. D. S. Davis, J. Plast. Film Sheeting 8, 101 (1992).
100. J. H. Grifth and B. G. Ranby, J. Polym. Sci. XXXVIII, 107 (1959).

101. F. J. Balta-Calleja
and C. G. Vonk, X-ray Scattering of Synthetic Polymers, Elsevier,
Amsterdam, 1989.
102. F. J. Padden Jr. and H. D. Keith, J. Appl. Phys. 37, 4013 (1966).
103. F. L. Binsbergen and B. G. M. deLange, Polymer 9, 23 (1968).
104. F. J. Padden Jr. and H. D. Keith, J. Appl. Phys. 44, 1217 (1973).
105. A. J. Lovinger, J. Polym. Sci., Polym. Phys. Ed. 21, 97 (1983).
106. D. R. Norton and A. Keller, Polymer 26, 704 (1985).
107. B. Lotz and J. C. Wittmann, J. Polym. Sci., Polym. Phys. Ed. 24, 1541 (1986).
108. F. J. Padden and H. D. Keith, J. Appl. Phys. 30, 1479 (1959).

Vol. 11

PROPYLENE POLYMERS

353

109. J. Varga, J. Mater. Sci. 27, 2557 (1992).

110. H. Awaya, Polymer 29, 591 (1988).
111. A. Lustiger, C. N. Marzinsky, and R. R. Mueller, J. Polym. Sci., Part B: Polym. Phys.
36, 2047 (1998).
112. M. Schumacher, A. J. Lovinger, P. Agarwal, J. C. Wittmann, and B. Lotz, Macromolecules 27, 6956 (1994).
113. A. Galambos, M. Wolkowicz, and R. Zeigler, in E. J. Vandenberg and J. C. Salamone,
eds., Catalysis in Polymer Synthesis, ACS Symposium Series, 496, 1991.
114. Z-G. Wang, R. A. Phillips, and B. S. Hsiao, J. Polym. Sci., Part B: Polym. Phys. 39,
1876 (2001).
115. J. Schmidtke, G. Strobl, and T. Thurn-Albrecht, Macromolecules 30, 5804 (1997).
116. P. Supaphol, J. E. Spruiell, and J. S. Lin, Polym. Int. 49, 1473 (2000).
117. A. J. Lovinger, D. D. Davis, and B. Lotz, Macromolecules 24, 552 (1991).
118. J. Rodriquez-Arnold, A. Zhang, S. Z. D. Cheng, A. J. Lovinger, E. T. Hsieh, P. Chu,
T. W. Johnson, K. G. Honnell, R. G. Geerts, S. J. Palackal, G. R. Hawley, and M. B.
Welch, Polymer 35, 1884 (1994).
119. J. Kressler, in J. Karger-Kocsis, ed., Polypropylene an A-Z Reference, Kluwer Academic
Publishers, Dordrecht, the Netherlands, 142, 1999.
120. P. Supaphol and J. E. Spruiell, Polymer 41, 1205 (2000).
121. R. Phillips, G. Hebert, J. News, and M. Wolkowicz, Polym. Eng. Sci. 34, 1731 (1994).
122. R. J. Samuels, Structured Polymer Properties: The Identication, Interpretation, and
Application of Crystalline Polymer Structure, John Wiley & Sons, Inc., New York,
1974.
123. A. Peterlin, Polym. Eng. Sci. 17, 183 (1977).
124. A. Peterlin, Colloid Polym. Sci. 265, 357 (1987).
125. M. F. Butler, A. M. Donald, and A. J. Ryan, Polymer 39, 39 (1998).
126. I. Karacan, A. K. Taraiya, D. I. Bower, and I. M. Ward, Polymer 34, 2692 (1993).
127. M. Cakmak, J. E. Spruiell, J. L. White, and J. S. Lin, Polym. Eng. Sci. 27, 893 (1987).
128. P. Galli, Macromol. Symp. 78, 269 (1994).
129. R. Galvan and M. Tirrell, Chem. Eng. Sci. 41, 2385 (1986).
130. W. R. Schmeal and J. R. Street, AIChE J. 17, 1188 (1971).
131. E. J. Nagel, V. A. Kirillov, and W. H. Ray, Ind. Eng. Chem., Prod. Res. Dev. 19, 372
(1980).
132. S. Floyd, K. Y. Choi, T. W. Taylor, and W. H. Ray, J. Appl. Polym. Sci. 32, 2935 (1986).
133. M. A. Ferrero and M. G. Chiovetta, Polym. Eng. Sci. 27, 1436 (1987).
134. M. A. Ferrero and M. G. Chiovetta, Polym. Eng. Sci. 31, 904 (1991).
135. R. A. Hutchinson, C. M. Chen, and W. H. Ray, J. Appl. Polym. Sci. 44, 1389 (1992).
136. E. L. Hoel, C. Cozewith, and G. D. Byrne, AIChE J. 40, 1669 (1994).
137. T. F. McKenna, J. Dupuy, and R. Spitz, J. Appl. Polym. Sci. 57, 3731 (1995).
138. L. Noristi, E. Marchetti, G. Baruzzi, and P. Sgarzi, J. Polym. Sci., Polym. Chem. Ed.
32, 3047 (1994).
139. M. A. Ferrero, E. Kof, R. Sommer, and W. C. Conner, J. Polym. Sci., Polym. Chem.
Ed. 30, 2131 (1992).
140. E. Martuscelli, M. Pracella, and A. Zambelli, J. Polym. Sci., Polym. Phys. Ed. 18, 619
(1980).
141. B. Wunderlich, Macromolecular Physics, Vol. 3, Academic Press, Inc., New York, 1980.
142. E. Martuscelli, M. Pracella, and L. Crispino, Polymer 24, 693 (1983).
143. J. J. Janimak, S. Z. D. Cheng, A. Zhang, and E. T. Hsieh, Polymer 33, 729 (1992).
144. R. Paukkeri and A. Lehtinen, Polymer 34, 4083 (1993).
145. K. D. Hungenberg, J. Kerth, F. Langhauser, B. Marczinke, and R. Schlund, in G. Fink,
R. Mulhaupt, and H. H. Brintzinger, eds., Ziegler Catalysts, Springer-Verlag, Berlin,
1995, p. 363.

354

PROPYLENE POLYMERS

Vol. 11

146. J. C. Haylock, R. A. Phillips, and M. D. Wolkowicz, in J. Scheirs and W. Kaminsky,

eds., Metallocene-Based Polyolens: Preparation, Properties and Technology, Vol. 2,
John Wiley & Sons, Inc., New York, 2000, p. 333.
147. J. Xu, S. Srinivas, and H. Marand, Macromolecules 31, 8230 (1998).
148. U. Gauer and B. Wunderlich, J. Chem. Phys. Ref. Data 10, 1051 (1981).
149. E. B. Bond, J. E. Spruiell, and J. S. Lin, J. Polym. Sci., Part B: Polym. Phys. 37, 3050
(1999).
150. H. S. Bu, S. Z. D. Cheng, and B. Wunderlich, Makromol. Chem. Rapid Commun. 9, 75
(1988).
151. F. Bai, F. Li, B. H. Calhoun, R. P. Quirk, and S. Z. D. Cheng, in J. Brandrup, E. H.
Immergut, E. A. Grulke, eds., Polymer Handbook, 4th ed., John Wiley & Sons, Inc.,
New York, 1999.
152. C. DeRosa, G. Talarico, L. Caporaso, F. Auriemma, M. Galimberti, and O. Fusco,
Macromolecules 31, 9109 (1998).
153. Y. Z. Wang, W. J. Chia, K. H. Hsieh, and H. C. Tseng, J. Appl. Polym. Sci. 44, 1731
(1992).
154. K. H. Hsieh and Y. Z. Wang, Polym. Eng. Sci. 30, 476 (1990).
155. Pro-fax Polypropylene Chemical Resistance, Montell Polyolens Technical Bulletin
TL-101, 1996.
156. D. DelDuca and E. P. Moore Jr., in E. P. Moore Jr., ed., Polypropylene Handbook,
Hanser, Munich, 1996.
157. R. F. Becker, L. P. J. Burton, and S. E. Amos, in E. P. Moore Jr., ed., Polypropylene
Handbook, Hanser, Munich, 1996.
158. T. S. Dziemianowicz and W. W. Cox, SPE ANTEC 85 540 (1985).
159. M. Gahleitner, J. Wolfschwenger, C. Bachner, K. Bernreitner, and W. Neil, J. Appl.
Polym. Sci. 61, 649 (1996).
160. T. Simonazzi, A. DeNicola, M. Aglietto, and G. Ruggeri, in S. Laggarwal, and W. Russo,
eds., Comprehensive Polymer Science, 1st suppl. Pergamon Press, Oxford, 1992.
a,
in J. Scheirs and W. Kaminsky, eds., Metallocene-Based
161. B. Lofgren and J. Seppal
Polyolens: Preparation, Properties and Technology, Vol. 2, John Wiley & Sons, Inc.,
New York, 2000, p. 143.
162. D. O. Geymer, in M. Dole, ed., The Radiation Chemistry of Macromolecules, Vol. 2,
Academic Press, Inc., New York, 1973.
163. A. J. DeNicola, A. F. Galambos, and M. D. Wolkowicz, ACS PMSE Polym. Prep. 67,
106 (1992).
164. C. E. Ruiz and R. T. LeNoir, in E. P. Moore Jr., ed., Polypropylene Handbook, Hanser,
Munich, 1996.
165. Montell Polyolens Resin Data Sheets, 1996. Adapted.
166. R. B. Lieberman and D. DelDuca, Proc. SPE Retec: Polyolens VIII, 21 (1993); Plast.
World 4, 4 (1989).
167. U. S. Pat. 5,173,540 (Dec. 22, 1992), J. Saito and A. Sampei (to Chisso Corp.).
168. Basell Polyolens Resin Data Sheets, 2000. Adapted.
169. U. S. Pat. 3,112,200 (Nov. 26, 1963) (to Montecatini).
170. U. S. Pat. 3,112,301 (Nov. 26, 1963) (to Montecatini).
171. G. Natta, Atti Accad. Naz. Lincei Rend. Classe Sci. Fis. Mat. Nat. Sez 3a 84, 61 (1955).
172. G. Natta, P. Pino, P. Corradini, F. Danusso, E. Mantica, and G. Moraglio, J. Am. Chem.
Soc. 77, 1708 (1955).
173. G. Natta, J. Polym. Sci. 16, 143 (1955).
174. G. Natta, Angew. Chem. 76, 430 (1955).
175. Belg. Pat. 533,362 (Nov. 16, 1953) (to Karl Ziegler).
176. W. Klemm and E. Krose, Z. Anorg. Chem. 253, 209 (1947).
177. G. Natta, P. Corrandini, and G. Allegra, J. Polym. Sci. 51, 399 (1961).

Vol. 11

PROPYLENE POLYMERS

355

178. M. Sittig, Polyolen Production Processes, Noyes Data Co., Park Ridge, N.J., 1976.
179. J. Boor, ZieglerNatta Catalysts and Polymerization, Academic Press, Inc., New York,
1979.
180. U. S. Pat. 3,051,690 (July 29, 1955) (to Hercules).
181. U. S. Pat. 3,128,252 (Aug. 15, 1956) (to Esso Research and Engineering Co.).
182. Brit. Pat. 1,092,390 (Apr. 27, 1966) (to Mitsubishi).
183. Ger. Offen. 2,213,086 (Oct. 5, 1972) (to Solvay & Cie).
184. L. A. M. Rodriguez and H. M. VanLooy, J. Polym. Sci., Part A1 4, 1971 (1966).
185. N. B. Chumaevskii, Makromol. Chem. 177, 747 (1976).
186. Brit. Pat. 1,286,867 (Nov. 26, 1969) (Montecatini).
187. Belg. Pat. 785,332 (June 23, 1972) (Montedison).
188. Ger. Offen. 2,643,143 (Nov. 21, 1975) (Montedison and Mitsui Petrochemical Ind.).
189. Ger. Offen. 2,735,672 (Aug. 9, 1976) (Montedison).
190. Ger. Offen. 2,822,783 (May 25, 1977) (Montedison).
191. Ger. Offen. 2,828,887 (July 4, 1977) (Montedison).
192. Eur. Pat. 29,232 (Nov. 24, 1979) (Montedison).
193. P. Galli, In IUPAC International Symposium on Macromolecules, Florence, Italy, IUPAC, 1980.
194. G. Natta, I. Pasquon, and A. Zambelli, J. Am. Chem. Soc. 84, 1488 (1962).
195. A. Zambelli, and co-workers, J. Polym. Sci., Part C 16, 2485 (1967).
196. U. Giannini, U. Zucchini, and E. Albizzati, J. Polym. Sci., Part B 8, 405 (1970).
197. D. G. H. Ballard, Adv. Catal. 23, 263 (1973).
198. U. S. Pat. 3,023,513 (May 1, 1962) (Esso Research and Engineering Co.).
199. U. S. Pat. 3,424,774 (Jan. 28, 1969) (Esso Research and Engineering Co.).
200. E. Tornquist and coworkers, J. Catal. 8, 189 (1967).
201. Z. W. Wilchinsky, R. W. Looney, and E. Tornquist, J. Catal. 28, 351 (1973).
202. Brit. Pat. 2,000,514 (July 3, 1978) (Montedison).
203. P. C. Barbe, G. Cecchin, and L. Noristi, eds. Advances in Polymer Science, Vol. 81,
Springer-Verlag, Berlin, 181, 1987.
204. K. Soga and coworkers, Polym. J. 5(2), 128 (1973).
205. E. Suzuki and coworkers, Makromol. Chem. 180, 2275 (1979).
206. U. Giannini, Makromol. Chem. Suppl. 5, 216 (1981).
207. N. Kashiwa, and J. Yoshitake, Makromol. Chem. Rapid Commun. 3, 211214 (1982).
208. P. C. Barbe and coworkers, Makromol. Chem., Rapid Commun. 4, 249252 (1983).
209. G. DiDrusco and R. Rinaldi, Hydrocarbon Process 63(11), 113 (1984).
210. N. Kashiwa and J. Yoshitake, Makromol. Chem. 185, 11331138 (1984).
211. R. Spitz, J. L. Lacombe, and A. Guyot, J. Polym. Sci., Polym. Chem. Ed. 22,
2641 (1984).
212. R. Spitz, J. L. Lacombe, and A. Guyot, J. Polym. Sci., Chem. Ed. 22, 2625 (1984).
213. T. Keii, Kinetics of ZieglerNatta Polymerization, Kodanska, Chapman and Hall, London, 1972.
214. I. Pasquon and U. Giannini, in J. R. Anderson and M. Boudart, eds. Catalysts, Science
and Technology, Springer-Verlag, Berlin, 1984.
215. K. Y. Choi and W. H. Ray, J. Appl. Polym. Sci. 30, 1065 (1985).
216. N. F. Brockmeier, and J. B. Rogan, Ind. Eng. Chem. Prod. Res. Dev. 24, 278 (1985).
217. T. Keii and coworkers, Makromol. Chem. 183, 22852304 (1982).
218. Y. Doi and coworkers, Ind. Eng. Chem. Prod. Res. Dev. 21, 580 (1982).
219. V. A. Zakharov, G. D. Bukatov, and Y. I. Yermakov, Polym. Sci. Technol. Coord. Polym.
19, 267 (1983).
220. G. Natta and I. Pasquon, Adv. Catal. 11, 165 (1959).
221. N. M. Chirkov, Proceedings of the IUPAC International Macromolecules Symposium,
Bucharest, Romania, IUPAC, 1969.

356

PROPYLENE POLYMERS

Vol. 11

222. C. D. Nentizescu, C. Huch, and A. Huch, Angew. Chem. 68, 438 (1956).
223. D. B. Ludlum, A. W. Anderson, and C. E. Ashby, J. Am. Chem. Soc. 80,
1380 (1958).
224. G. Natta and coworkers, Chim. Ind. Milan 38, 124 (1956).
225. A. Zambelli and coworkers, Macromolecules 13, 798 (1980).
226. P. Cossee, Tetrahedron Lett. 17, 12 (1960).
227. P. Cossee, Proceedings of the International Congress on Coordination Chemistry, 1961,
p. 241.
228. P. Cossee, J. Catal. 3, 8088 (1964).
229. T. Miyazawa and Y. Ideguchi, J. Polym. Sci. Polym. Lett. 1, 389 (1963); A. Zambelli,
M. G. Giongo, and G. Natta, D. Makromol. Chem. 112, 183 (1968); A. Zambelli and
C. Tosi, Adv. Polym. Sci. 15, 32 (1974).
230. E. J. Arlman and P. Cossee, J. Catal. 3, 99 (1964).
231. A. Zambelli, P. Locatelli, and E. Rigamonti, Macromolecules 12, 156 (1979).
232. A. Zambelli, NMR Basic Principles and Progress, Springer, Berlin, 1971, p. 101.
233. P. C. Barbe, L. Noristi, and G. Baruzzi, Makromol. Chem. 193, 229241 (1992).
234. U. S. Pat. 4,971,937 (to HIMONT).
235. P. Pino and coworkers, in J. C. W. Chein, ed., Coordination Polymerization, 1975,
Academic Press, Inc.: New York. p. 25.
236. P. Pino, Adv. Polym. Sci. 4, 393 (1965).
237. P. Pino and G. P. Lorenzi, Chim. Ind. Milan 42, 712 (1960).
238. P. Pino and coworkers, J. Am. Chem. Soc. 84, 1487 (1962).
239. P. Pino, F. Ciardelli, and G. P. Lorenzi, J. Polym. Sci., Part C 4, 21 (1963).
240. P. Pino and coworkers, in Proceedings of the International Symposium Transition
Metal Catalyzed PolymerizationUnsolved Problems, Midland, Mich., 1981.
241. P. Corradini, V. Barone, and R. Fusco, Gazzetta Chimica Italiana 113, 601607
(1983).
242. P. Corradini, V. Busico, and G. Guerra, in S. G. Allen, ed. Comprehensive Polymer
Science, Pergamon Press, New York, 1988, p. 2948.
243. A. Zambelli, in J. C. W. Chien, ed., Coordination Polymerization, Academic Press, Inc.,
New York. p. 15, 1975.
244. P. Locatelli, A. Immirzi, and A. Zambelli, Makromol. Chem. 176, 1121 (1975).
245. G. Morini and coworkers, Macromolecules 29, 57705776 (1996).
246. M. C. Sacchi and coworkers, Macromolecules 29, 33413345 (1996).
247. L. Noristi, P. C. Barbe, and G. Baruzzi, Makromol. Chem. 192, 11151127 (1991).
248. E. Iiskola, P. Sormunen, and T. Garoff, W. Kaminsky and H. Sinn, eds., Transition
Metals and Organometallics as Catalysts for Olen Polymerization, Springer-Verlag,
Berlin, 1988, pp. 113122.
249. T. Okano and coworkers, Stud. Surf. Sci. Catal. Olen Polym. 1990. p. 177183.
onen, L. Kuutti, and J. V. Seppal
a,
Makromol. Chem. 193, 14131421 (1992).
250. M. Hark
251. R. Spitz and coworkers, Makromol. Chem. 190, 717723 (1989).
252. I. W. Parsons and T. M. Al-Turki, Polymer Commun. 30(3), 7273 (1989).
253. M. Kioka and N. Kashiwa, J. Macromol. Sci. Chem. A 28, 865873 (1991).
254. K. Imaoka and coworkers, J. Mol. Catal. 82, 3744 (1993).
255. J. C. Chadwick, A. Miedema, and O. Sudmeijer, Macromol. Chem. Phys. 195,
167172 (1994).
256. J. C. Chadwick in Polyolens 2000 International Conference on Polyolens Society of
Plastics Engineers. Society of Plastics Engineers, Houston, Tex., 2000.
257. E. Albizzati and coworkers, Macromol. Symp. 89, 7389 (1995).
258. K. Soga, T. Shinon, and Y. Doi, Makromol. Chem. 189, 1531 (1988).
259. J. C. Chadwick and coworkers, Macromol. Chem. Phys. 197, 25012510 (1996).
260. J. C. Chadwick, Macromol. Symp., 2001.

Vol. 11
261.
262.
263.
264.
265.
266.
267.
268.
269.
270.
271.
272.

273.
274.
275.
276.
277.
278.
279.
280.
281.
282.
283.
284.
285.
286.
287.
288.
289.
290.
291.
292.
293.
294.
295.
296.
297.
298.
299.

PROPYLENE POLYMERS

357

W. Kaminsky, Rapra Rev. Rep. 10, 1135 (1999).

W. Spaleck and coworkers, Organometallics 13, 954963 (1994).
S. Miyake, Y. Okumura, and S. Inazawa, Macromolecules 28, 30743079 (1995).
H. R. Blum, in MetCon 2000, Polymers in Transition Platforms in Single-Site Catalysis, Houston, Tex., 2000.
G. DiDrusco and R. Rinaldi, Hydrocarbon Process. 60(5), 153 (May 1981).
U. S. Pat. 3,051,690 (July 29, 1955), E. J. Vandenberg (to Hercules Powder Co.).
Brit. Pat. 1,044,811 (Apr. 9, 1962) (to Rexall Drug and Chemical Co.).
U.S. Pat. 3,476,729 (Nov. 4, 1969), D. E. Smith, R. M. Keeler, and E. Guenther (to
Phillips Petroleum).
J. F. Ross and W. A. Bowles, Ind. Eng. Chem. Prod. Res. Dev. 24, 149 (1985).
Oil Gas J. 68, 64 (1970).
Ger. Offen. 2,213,086 (Oct. 5, 1972), J. P. Hermans (to Solvay & Cie SA).
Ger. Offen. 2,643,143 (Nov. 21, 1975) (to Montedison and Mitsui Petrochemical); Ger.
Offen. 2,735,672 (Aug. 9, 1976), U. Giannini, E. Albizzati, and S. Parodi (to Montedison
and Mitsui Petrochemical); Ger. Offen. 2,822,783 (May 25, 1977), U. Scata, L. Luciani,
and P. C. Barbe (to Montedison); U. S. Pat 4,069,169 (Jan. 17, 1978), N. Kashiwa and
A. Toyota (to Mitsui Petrochemcial).
G. DiDrusco and R. Rinaldi, Hydrocarbon Process. 63(11), 116 (Nov. 1984).
Hydrocarbon Process 72(3), 204 (1993).
C. Cipriani and C. A. Trishman Jr., Chem. Eng. 80, (Apr. 20, 1981).
Plast. World 51(6), 12 (1993).
Z. Tadmor and C. G. Gogos, Principles of Polymer Processing, John Wiley & Sons, Inc.,
New York, 1979.
M. R. Kantz and H. D. Newman Jr., F. H. Stigale, J. Appl. Polym. Sci. 16, 1249
(1972).
D. R. Fitchmun and Z. Mencik, J. Polym. Sci., Polym. Phys. Ed. 11, 951 (1973).
M. Fujiyama, H. Awaya, and S. Kimura, J. Appl. Polym. Sci. 21, 3291 (1977).
M. Fujiyama and S. Kimura, J. Appl. Polym. Sci. 22, 1225 (1978).
M. Fujiyama and K. Azuma, J. Appl. Polym. Sci. 23, 2807 (1979).
S. S. Katti and J. M. Schultz, Polym. Eng. Sci. 22, 1001 (1982).
M. Fujiyama and T. Wakino, J. Appl. Polym. Sci. 43, 57 (1991).
M. Fujiyama and T. Wakino, J. Appl. Polym. Sci. 43, 97 (1991).
M. Fujiyama, Int. Polym. Proc. 8, 245 (1993).
P. Ramanini, Rheol. Acta 21, 699 (1982).
V. Bansal and R. L. Shambaugh, Polym. Eng. Sci. 36, 2785 (1996).
A. Winter, SPO 97 Proc. 1 (1997).
J. J. McAlpin, C. Y. Cheng, D. A. Plank, and G. A. Stahl, INSIGHT 95 Proc.
(1995).
A. Ahmed, Polypropylene Fibers-Science and Technology, Elsevier, Amsterdam,
1982.
J. R. Beren and C. Capellman, paper presented at SAE International Congress,
1994.
K. E. McHugh and K. Ogale, SPE ANTEC 90 452 (1990).
J. Foster, in Modern Plastics Encyclopedia 1983-1984, Vol. 60 (10A), McGraw-Hill,
New York, 1983, p. 328.
K. T. Johansson, Proc. SPE Retec: Polyolens 8, 334 (1993).
S. Al-Malaika and G. Scott, in N. S. Allen, ed., Degradation and Stabilization of Polyolens, Applied Science Publishers Ltd., London, 1983, p. 247.
C. Armstrong, M. J. Husbands, and G. Scott, Eur. Polym. J. 15, 241 (1979).
Society of the Plastics Industry, Facts and Figures 1999.
A. H. Tullo, Chem. Eng. News 79, 1214 (Feb. 5, 2001).

358

PROPYLENE POLYMERS

Vol. 11

300. Mod. Plast. 2229 (Feb. 2002); 4449 (Feb. 2001); 4879 (Feb. 2000); 7280 (Jan.
1999); 7482 (Jan. 1998); 56, 7684 (Jan. 1997); 54, 7078 (Jan. 1996); 6368
(Jan. 1995).
301. American Plastics Council Plastics Industry Producers Statistics Group, as compiled
by VERIS Consulting, LLC.
302. Asia Chem. News 1421 (June 11, 2001).
303. Mod. Plast. 54 (Jan. 1999).
304. Chemical Market Resources Inc., CMR Polym. Tracker 5, 25 (Apr. 2000).
305. Mod. Plast. 2229 (Feb. 2002).

RICHARD LIEBERMAN
Basell R&D Center
CONSTANTINE STEWART

PROTEIN FOLDING.
PSA.

See PRESSURE SENSITIVE ADHESIVES.

PULTRUSION.
PVC.
PVDC.

See Volume 7.

See COMPOSITES, FABRICATIOIN.

See VINYL CHLORIDE POLYMERS.

See VINYLIDENE CHLORIDE POLYMERS.

PVF.

See VINYL FLUORIDE POLYMERS.

PVK.

See VINYLCARBAZOLE POLYMERS.

PVP.

See VINYL AMIDE POLYMERS.